Polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants

ABSTRACT

The present invention relates to a polymeric material comprising units capable of having a cationic charge at a pH of from about 4 to about 12; provided that said polymeric material has an average cationic charge density from about 2.75 or less units per 100 daltons molecular weight at a pH of from about 4 to about 12. The polymeric material is a suds enhancer and a suds volume extender for hand dishwashing compositions and personal care products such as soaps, shaving cream foam, foaming shaving gel, foam dephiliatories and shampoos. The polymers are also effective as a soil release agent in fabric cleaning compositions. The polymers are also useful in agrochemical foam, fire-fighting foam, hard surface cleaner foam, and coagulant for titanium dioxide in paper making.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.09/318,941 filed May 26, 1999, incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to polymers and compositions and methodsof use for polymers in beauty care and personal care products as well asin fabric detergent. More particularly, the polymers suitable for use inthe compositions and methods of the present invention comprise cationic,anionic, and noncharged monomer units, or units having mixtures thereof.In particular, the polymers have an average cationic charge density of2.77 or less, preferably from about 0.01 to about 2.75, more preferablyfrom about 0.1 to about 2.75, most preferably from about 0.75 to about2.25 units per 100 daltons molecular weight at a pH of from about 4 toabout 12.

The present polymers are useful in compositions for providing enhancedsuds volume and suds duration during hand dishwashing. The presentinvention further relates to compositions, and methods for using oilwell foam, fire-fighting foam, agrochemical foam, coagulant for titaniumdioxide, shower rinse, and hard surface cleaner foam

U.S. patent application Ser. No. 09/318,941, filed May 26, 1999, andPatent Cooperation Treaty application serial no. PCT/US00/14456, filedMay 25, 2000 are incorporated herein by reference.

BACKGROUND OF THE INVENTION

Compositions for foam stabilizing, titanium dioxide coagulantion andshower rinses are called upon to perform under difficult conditions.

For example liquid detergent compositions which are suitable for handdishwashing must satisfy several criteria in order to be effective.These compositions must be effective in cutting grease and greasy foodmaterial and once removed, must keep the greasy material fromre-depositing on the dishware.

The presence of suds in a hand dishwashing operation has long been usedas a signal that the detergent continues to be effective. However,depending upon the circumstances, the presence of suds or the lackthereof, has no bearing upon the efficacy of liquid detergents.Therefore, the consumer has come to rely upon a somewhat erroneoussignal, the lack or absence of soap suds, to indicate the need foradditional detergent. In many instances the consumer is adding anadditional amount of detergent far in excess of the amount necessary tothoroughly clean the dishes. This wasteful use of detergent isespecially true in hand dishwashing since the soiled cooking articlesare usually cleaned in a “washing difficulty” queue, for example,glasses and cups, which usually do not contact greasy food, are washedfirst, followed by plates and flatware, and finally pots and pans whichcontain the most residual food material and are usually, therefore, the“greasiest”.

The lack of suds in the dishwater when pots and pans are usuallycleaned, together with the visual inspection of the amount of residualfood material on the cookware surface, typically compels the consumer toadd additional detergent when a sufficient amount still remains insolution to effectively remove the soil and grease from the dishware orcookware surface. However, effective grease cutting materials do notnecessarily produce a substantial amount of corresponding suds.

Accordingly, there remains a need in the art for liquid dishwashingdetergents useful for hand washing dishware which have an enduring sudslevel while maintaining effective grease cutting properties. The needexists for a composition, which can maintain a high level of suds aslong as the dishwashing composition is effective. Indeed, there is along felt need to provide a hand dishwashing composition which can beuse efficiently by the consumer such that the consumer uses only thenecessary amount of detergent to fully accomplish the cleaning task.

There is also a need for products in the laundry field for a producthaving improved grease and soil removal properties. There is also a needfor products in the personal care field, particularly hand soaps, bodywashes, shampoos, shaving creams, shaving gels and dephiliatories, whichhave improved foam retention. There is also a need for improved oil welltreating foam, agrochemical foam, fire-fighting foam, shower rinses andcoagulants for TiO₂.

SUMMARY OF THE INVENTION

The present invention meets the aforementioned needs in that it has beensurprisingly discovered that polymeric materials having the capacity toaccommodate a positive charge character, negative charge character, orzwitterionic character have the capacity to provide liquid hand washdetergent compositions with extended suds volume and suds durationbenefits.

In one aspect of the present invention, there are provided compositionshaving increased suds volume and suds retention suitable for use in handdishwashing, or other uses. The compositions comprise:

-   -   a) an effective amount of a polymeric suds/foam stabilizer        (suds/foam booster), said stabilizer comprising:        -   i) units capable of having a cationic charge at a pH of from            about 4 to about 12; provided that said suds stabilizer has            an average cationic charge density of 2.77 or less,            preferably from about 0.01 to about 2.75, more preferably            from about 0.1 to about 2.75, most preferably from about            0.75 to about 2.25 units per 100 daltons molecular weight at            a pH of from about 4 to about 12;    -   b) an effective amount of a surfactant for the given use; and    -   c) the balance carriers and other adjunct ingredients; provided        that a 10% aqueous solution of said composition has a pH of from        about 4 to about 12, is provided.

In another aspect of the present invention, compositions havingincreased suds/foam volume and suds/foam retention suitable for use inhand dishwashing, or other foaming uses said compositions comprising:

-   -   a) an effective amount of a polymeric suds/foam stabilizer        (suds/foam booster), said stabilizer comprising:        -   i) one or more units capable of having a cationic charge at            a pH of from about 4 to about 12; and        -   ii) one or more units having one or more hydroxyl groups;            provided that said suds stabilizer has a hydroxyl group            density of from about 0.2 to about 100; and        -   iii) optionally, one or more other monomeric units described            hereinafter;            -   provided that said suds/foam stabilizer has an average                cationic charge density of 2.77 or less (or the                above-listed preferred ranges); and    -   b) an effective amount of a surfactant for the given use (for        example a detersive surfactant for a use related to cleaning);        and    -   c) the balance carriers and other adjunct ingredients;        provided that a 10% aqueous solution of said composition has a        pH of from about 4 to about 12.

Typically, these compositions are granular solids or liquid, preferablyliquid. Moreover, for many of the purposes for which these compositionsare intended, the surfactant comprises a detergent surfactant.

In yet another aspect of the present invention, there are providedliquid detergent compositions having increased suds volume and sudsretention suitable for use in hand dishwashing, said compositionscomprising:

-   -   a) an effective amount of a polymeric suds stabilizer (suds        booster), said stabilizer comprising:        -   i) one or more units capable of having a cationic charge at            a pH of from about 4 to about 12; and        -   ii) one or more units having one or more hydrophobic groups,            preferably the hydrophobic groups are selected from the            group consisting of non-hydroxyl groups, non-cationic            groups, non-anionic groups, non-carbonyl groups, and/or            non-H-bonding group, more preferably the hydrophobic groups            are selected from the group consisting of alkyls,            cycloalkyls, aryls, alkaryls, aralkyls and mixtures thereof;        -   iii) optionally, one or more other monomeric units described            hereinafter;    -    provided that said suds stabilizer has an average cationic        charge density of 2.77 or less (or the above-listed preferred        ranges);    -   b) an effective amount of a surfactant, typically a detersive        surfactant; and    -   c) the balance carriers and other adjunct ingredients; provided        that a 10% aqueous solution of said composition has a pH of from        about 4 to about 12.

In still another aspect of the present invention, methods for providingincreased suds retention and suds volume when hand washing dishware isprovided.

In still another aspect, the present invention provides methods andcompositions for personal care, such as shampoos, soaps, shaving creamfoam, shaving gel, and diphiliatories, oil field foam, fire fightingfoam, agrochemical foam, hard surface (e.g., bathroom tile) foamcleaner, shower rinse, fabric detergents with improved soil releaseproperties, and coagulants/retention aids for titanium dioxide used inpaper processing.

These and other objects, features and advantages will become apparent tothose of ordinary skill in the art from a reading of the followingdetailed description and the appended claims.

All percentages, ratios and proportions herein are by weight, unlessotherwise specified. All temperatures are in degrees Celsius (° C.)unless otherwise specified. All documents cited are in relevant part,incorporated herein by reference in their entirety.

Additional background on these compositions and methods is provided byPCT Patent Application Nos. PCT/US98/24853, PCT/US98/24707,PCT/US98/24699 and PCT/US98/24852, all incorporated herein by referencein their entirety.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to polymeric materials, which provideenhanced suds/foam duration and enhanced suds/foam volume whenformulated into liquid compositions suitable in the field of personalcare, particularly for hand washing and/or body washing soaps,shampooing, shaving gel foam, dephiliatories, agrochemical foams, oilwell foams, fire fighting foams, and hard surface cleaner foams. Thepolymeric materials are also useful as coagulants for treatment oftitanium dioxide in paper plants and useful in shower rinses forbathroom use. Among their other advantages, they also provide enhancedsoil release for laundry detergents for use in washing machines.

The polymeric material may comprise any material provided the finalpolymers have an average cationic charge density of 2.77 or less,preferably from about 0.01 to about 2.75, more preferably from about 0.1to about 2.75, most preferably from about 0.75 to about 2.25 units per100 daltons molecular weight at a pH of from about 4 to about 12.

The compositions of the present invention comprise:

-   -   a) an effective amount of a polymer, e.g., polymeric suds/foam        stabilizer, said polymer comprising:        -   i) units capable of having a cationic charge at a pH of from            about 4 to about 12;    -    provided that said polymer, has an average cationic charge        density of 2.77 or less, preferably from about 0.01 to about        2.75, more preferably from about 0.1 to about 2.75, most        preferably from about 0.75 to about 2.25 units per 100 daltons        molecular weight at a pH of from about 4 to about 12;    -   b) an effective amount of a surfactant for the selected use; and    -   c) the balance carriers and other adjunct ingredients;    -   provided that a 10% aqueous solution of said detergent        composition has a pH of from about 4 to about 12.

It is preferred that the polymer (a) further comprises one or more ofthe following:

-   -   ii) one or more units having one or more hydroxyl groups,        provided that the polymer has a hydroxyl group density of about        0.5 or less, more preferably from about 0.0001 to about 0.4 as        measured by the Hydroxyl Group Density Equation as outlined in        greater detail below; and/or    -   iii) one or more units having one or more hydrophobic groups,        preferably the hydrophobic groups are selected from the group        consisting of non-hydroxyl groups, non-cationic groups,        non-anionic groups, non-carbonyl groups, and/or non-H-bonding        group, more preferably the hydrophobic groups are selected from        the group consisting of alkyls, cycloalkyls, aryls, alkaryls,        aralkyls and mixtures thereof.

It is desirable that the polymer (a) further optionally, but preferablycomprises one or more of the following:

-   -   iv) units capable of having an anionic charge at a pH of from        about 4 to about 12;    -   v) units capable of having an anionic charge and a cationic        charge at a pH of from about 4 to about 12;    -   vi) units having no charge at a pH of from about 4 to about 12;        and    -   vii) mixtures of units (iv), (v), (vi), and (vii).

The polymers of the present invention may be random or block polymers.

The following describes non-limiting examples of polymeric materialwhich may be suitable for use in the present invention.

Polymeric Enhancing Agents

The polymers of the present invention are useful as suds/foamstabilizers, soil release agents, coagulants, and shower rinse enhancersand are hereinafter termed “polymeric enhancing agents.” These polymersof the present invention contain units capable of having a cationiccharge at a pH of from about 4 to about 12, provided that the polymericenhancing agent have an average cationic charge density of 2.77 or less,preferably from about 0.01 to about 2.75, more preferably from about 0.1to about 2.75, most preferably from about 0.75 to about 2.25 units per100 daltons molecular weight at a pH of from about 4 to about 12.

Preferably, the polymeric enhancing agents also include units capable ofinfluencing the average cationic charge density of the polymericenhancing agents, preferably by decreasing the average cationic chargedensity of the polymeric enhancing agents. Such units capable ofinfluencing the average cationic charge density of the polymericenhancing agents may, and preferably do, provide additional advantageousproperties to the polymeric suds stabilizers that increase theircleaning and/or suds boosting and/or suds retention properties. Further,such units may increase the interactions between the polymer, which isneutral or positively charged, and the soil which is negatively charged.

Additionally, the polymeric enhancing agents can be present as the freebase or as a salt. Typical counter ions include, acetate, citrate,maleate, sulfate, chloride, etc.

Further, the polymeric suds stabilizers of the present invention may becopolymers, terpolymers with random and/or repeating units, and/or blockpolymers such as di-, tri- and multi-block polymers.

For example a copolymer can be made from two monomers, G and H, suchthat G and H are randomly distributed in the copolymer, such as

-   -   GHGGHGGGGGHHG . . . etc.        or G and H can be in repeating distributions in the copolymer,        for example    -   GHGHGHGHGHGHGH . . . etc.,    -   or    -   GGGGGHHGGGGGHH . . . etc.,

The same is true of the terpolymer, the distribution of the threemonomers can be either random or repeating.

Cationic Units

For the purposes of the present invention the term “cationic unit” isdefined as “a moiety which when incorporated into the structure of thesuds stabilizers of the present invention, is capable of maintaining acationic charge within the pH range of from about 4 to about 12. Thecationic unit is not required to be protonated at every pH value withinthe range of about 4 to about 12.” Non-limiting examples of units whichcomprise a cationic moiety include the cationic units having theformula:

wherein each of R¹, R² and R³ are independently selected from the groupconsisting of hydrogen, C₁ to C₆ alkyl, and mixtures thereof, preferablyhydrogen, C₁ to C₃ alkyl, more preferably, hydrogen or methyl. T isselected from the group consisting of substituted or unsubstituted,saturated or unsaturated, linear or branched radicals selected from thegroup consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl,heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto,ester, ether, carbonyl, amido, amino, glycidyl, carbanato, carbamate,carboxylic, and carboalkoxy radicals and mixtures thereof. Z is selectedfrom the group consisting of: —(CH₂)—, (CH₂—CH═CH)—, —(CH₂—CHOH)—,(CH₂—CHNR⁴)—, —(CH₂—CHR⁵—O)— and mixtures thereof, preferably —(CH₂)—.R⁴ and R⁵ are selected from the group consisting of hydrogen, C₁ to C₆alkyl and mixtures thereof, preferably hydrogen, methyl, ethyl andmixtures thereof; z is an integer selected from about 0 to about 12,preferably about 2 to about 10, more preferably about 2 to about 6. A isNR⁶R⁷ or NR⁶R⁷R⁸. Wherein each of R⁶, R⁷ and R⁸, when present, areindependently selected from the group consisting of H, C₁-C₈ linear orbranched alkyl, alkyleneoxy having the formula:

(R⁹O)_(y)R¹⁰

wherein R⁹ is C₂-C₄ linear or branched alkylene, and mixtures thereof;R¹⁰ is hydrogen, C₁-C₄ alkyl, and mixtures thereof; y is from 1 to about10. Preferably R⁶, R⁷ and R⁸, when present, are independently, hydrogen,C₁ to C₄ alkyl. Alternatively, NR⁶R⁷ or NR⁶R⁷R⁸ can form a heterocyclicring containing from 4 to 7 carbon atoms, optionally containingadditional hetero atoms, optionally fused to a benzene ring, andoptionally substituted by C₁ to C₈ hydrocarbyl, and/or acetates.Examples of suitable heterocycles, both substituted and unsubstituted,are indolyl, isoindolinyl imidazolyl, imidazolinyl, piperidinylpyrazolyl, pyrazolinyl, pyridinyl, piperazinyl, pyrrolidinyl,pyrrolidinyl, guanidino, amidino, quinidinyl, thiazolinyl, morpholineand mixtures thereof, with morpholino and piperazinyl being preferred.Furthermore the polymeric suds stabilizer has a molecular weight of fromabout 1,000 to about 2,000,000 preferably from about 5,000 to about1,000,000, more preferably from about 10,000 to about 750,000, morepreferably from about 20,000 to about 500,000, even more preferably fromabout 35,000 to about 300,000 daltons. The molecular weight of thepolymeric suds boosters, can be determined via conventional gelpermeation chromatography or any other suitable procedure known to thoseof ordinary skill in the art.

Examples of the cationic unit of formula [I] include, but are notlimited to, the following structures:

A preferred cationic unit is 2-dimethylaminoethyl methacrylate (DMAM)having the formula:

Hydroxyl-Containing Units

The hydroxyl group density of a polymeric suds stabilizer/polymericenhancing agent of the present invention is determined by the followingcalculation.

${{Hydroxyl}\mspace{14mu} {Group}\mspace{14mu} {Density}} = \frac{\left( {{Molecular}\mspace{14mu} {Weight}\mspace{14mu} {of}\mspace{14mu} {Hydroxyl}\mspace{14mu} {Group}} \right)}{\left( {{Total}\mspace{14mu} {Monomer}\mspace{14mu} {Molecular}\mspace{14mu} {Weight}} \right)}$

For example, the Hydroxyl Group Density of a polymeric sudsstabilizer/polymeric enhancing agent containing 2-dimethylaminoethylmethacrylate having a molecular weight of approximately 157 andhydroxyethylacrylate having a molecular weight of approximately 116grams/mole, at a 1:3 mole ratio would be calculated as follows:

${{Hydroxyl}\mspace{14mu} {Group}\mspace{14mu} {Density}\mspace{14mu} \frac{17}{\left( {{3(116)} + 157} \right)}} = 0.0337$

Preferably, the polymeric enhancing agents of the present invention havea hydroxyl group density of about 0.5 or less, more preferably fromabout 0.0001 to about 0.4.

Nonlimiting examples of such hydroxyl group-containing units include,but are not limited to the following:

wherein n is an integer from 2 to 100, preferably 2 to 50, morepreferably 2 to 30.

Hydrophobic Units

Suitable hydrophobic group-containing units for use in the presentinvention include, but are not limited to, hydrophobic groups preferablyselected from the group consisting of non-hydroxyl groups, non-cationicgroups, non-anionic groups, non-carbonyl groups, and/or non-H-bondinggroups, more preferably selected from the group consisting of alkyls,cycloalkyls, aryls, alkaryls, aralkyls and mixtures thereof.

Nonlimiting examples of such hydrophobic group-containing units include,but are not limited to the following:

Hydrophilic Units

Suitable hydrophilic group-containing units for use in the presentinvention include, but are not limited to, hydrophilic groups preferablyselected from the group consisting of carboxyl groups, carboxylic acidsand their salts, sulfonic acids and their salts, heteroatom-containingmoieties present in a ring or linear form and mixtures thereof.

Nonlimiting examples of such hydrophilic group-containing units include,but are not limited to the following:

Anionic Units

For the purposes of the present invention, the term “anionic unit” isdefined as “a moiety which when incorporated into the structure of thesuds stabilizers/polymeric enhancing agents of the present invention, iscapable of maintaining an anionic charge within the pH range of fromabout 4 to about 12. The anionic unit is not required to bede-protonated at every pH value within the range of about 4 to about12.” Non-limiting examples of units which comprise a anionic moietyinclude, acrylic acid, methacrylic acid, glutamic acid, aspartic acid, amonomeric unit having the formula:

and a monomeric unit having the formula:

the latter of which also comprises a moiety capable of having a cationiccharge at a pH of about 4 to about 12. This latter unit is definedherein as “a unit capable of having an anionic and a cationic charge ata pH of from about 4 to about 12.”

Non-Charged Units

For the purposes of the present invention the term “non-charged unit” isdefined as “a moiety which when incorporated into the structure of thesuds stabilizers/polymeric enhancing agents of the present invention,has no charge within the pH range of from about 4 to about 12.”Non-limiting examples of units which are “non-charged units” aremonomers such as styrene, ethylene, propylene, butylene, 1,2-phenylene,esters, amides, ketones, ethers, and the like.

The units which comprise the polymers of the present invention may, assingle units or monomers, have any pK_(a) value.

Preferably, the polymeric suds stabilizers/polymeric enhancing agentsare selected from copolymers, which can optionally be crosslinked,terpolymers and other polymers (or multimers).

Particular Polymers

Preferred polymers of the present invention comprise:

-   -   A. at least one cationic monomeric unit A having a Formula I:

wherein

R¹ is H or an alkyl having 1 to 10 carbon atoms,

R² is a moiety selected from the group consisting of

wherein R³ is selected from the group consisting of

a is an integer from 0 to 16, preferably 0 to 10;b is an integer from 2 to 10;c is an integer from 2 to 10;d is an integer from 1 to 100;

R⁴ and R⁵ are independently selected from the group consisting of —H,and

R⁸ is independently selected from the group consisting of a bond and analkylene having 1 to 18, preferably 1 to 10, carbon atoms;

R⁹ and R¹⁰ are independently selected from the group consisting of —H,alkyl having 1 to 10, preferably 1 to 8 carbon atoms;

R¹² and R¹³ are independently selected from the group consisting of Hand alkyl having from 1 to 10, preferably 1 to 8 carbon atoms;

wherein x is an integer from 2 to 10;

-   -   B. at least one monomeric unit B selected from the group        consisting of: a monomeric unit of Formula W

wherein R²⁰ is selected from the group consisting of H and CH₃;

R²¹ is selected from the group consisting of:

wherein e is an integer from 3 to 25, preferably 3 to 5;

—O—(CH₂)_(f)CH₃

wherein f is an integer from 0 to 25, preferably 0 to 12;

wherein g is an integer from 1 to 100, preferably 1 to 50,

h is an integer from 1 to 100, preferably 1 to 50,

R²³ is —H, —CH₃ or —C₂H₅,

R²⁴ is —CH₃ or —C₂H₅;

wherein j is an integer from 1 to 25, preferably 2 to 12;

wherein k is an integer from 1 to 25, preferably 1 to 12;

—NH—(CH₂)_(m)—NH₂.HCl, wherein m is an integer from 1 to 25, preferably2 to 12; and

a polyhydroxy monomeric unit of Formula VI:

wherein n is an integer from 1 to 50, preferably 1 to 25; and

-   -   C. optionally at least one monomeric unit C selected from the        group consisting of:

wherein R²⁵ is —H or —CH₃,

wherein R²⁶ is —H or CH₃.

A preferred terpolymer and/or multimer of the present inventioncomprises at least one said monomeric unit A, at least one saidmonomeric unit B and at least one said monomeric unit C.

Preferably, at least one monomeric unit A is selected from the groupconsisting of:

wherein R³⁰ is H or —CH₃,wherein R³¹ is a bond or and

R³² and R³³ are —CH₃ or —C₂H₅.

Preferably, the polymer is a terpolymer in which:

said at least one monomeric unit B is selected from the group consistingof:

wherein R³⁸ is selected from the group consisting of H and CH₃ and

R⁴⁰ is selected from the group consisting of —CH₂CH₂—OH and

and isomers thereof,

said terpolymer comprising said at least one monomeric unit C,

wherein the molar ratio of said monomeric unit A: monomeric unit B:monomeric unit C is 1 to 9:1 to 9:1 to 6 respectively.

Preferably, the polymer has at least one monomeric unit B which has theformula:

wherein q ranges from 1 to 12, preferably 2 to 12, preferably 1 to 10,more preferably 1 to 9.

Preferably, the polymer is a terpolymer, in which at least one monomericunit A is selected from the group consisting of:

wherein R¹⁰ is H or CH₃,

R¹¹ is a bond or

and R¹² and R¹³ are —CH₃ or —C₂H₅, and said polymer comprises said atleast one monomeric unit C.

Preferably, the molar ratio of monomeric unit A: monomeric unit B:monomeric unit C ranges from 1 to 9:1 to 9:1 to 3 respectively.

Preferably, at least one monomeric unit A has a formula selected fromthe group consisting of:

Preferably, at least one monomeric unit A has a formula selected fromthe group consisting of:

Preferably, at least one one monomeric unit B is selected from the groupconsisting of:

wherein n is an integer from 2 to 50, preferably 2 to 30, morepreferably 2 to 27,

Specific Polymers

Nonlimiting examples of such copolymers, which can optionally becrosslinked, terpolymers and multimers have the following formulas:

Examples of preferred copolymers of the present invention are thefollowing:

Examples of preferred terpolymers of the present invention are thefollowing:

Examples of preferred multimers of the present invention are thefollowing:

The compositions according to the present invention comprise at least aneffective amount of the polymer described herein, preferably from about0.01% to about 10%, more preferably from about 0.001% to about 5%, mostpreferably from about 0.1% to about 2% by weight, of said composition.What is meant herein by “an effective amount polymeric suds stabilizers”is that the suds volume and suds duration produced by the presentlydescribed compositions are sustained for an increased amount of timerelative to a composition which does not comprise one or more of thepolymeric suds stabilizer described herein.

Additionally, the polymer can be present as the free base or as a salt.Typical counter ions include, acetate, citrate, maleate, sulfate,chloride, etc.

For other uses of these polymers, e.g., personal care, shampoo, soap,shaving cream, shaving gel, diphiliatories, oil field foam, firefighting foam, agrochemical foam, hard surface (e.g., bathroom tile)foam cleaner, and coagulants/retention aids for titanium dioxide used inpaper production. The effective amounts for each use are the amountswhich result in an improvement in the desired property in comparisonwith a composition lacking the polymer.

Proteinaceous Suds Stabilizers

The proteinaceous suds stabilizers of the present invention can bepeptides, polypeptides, amino acid containing copolymers, terpolymersetc., and mixtures thereof. Any suitable amino acid can be used to formthe backbone of the peptides, polypeptides, or amino acid, wherein thepolymers have an average cationic charge density of 2.77 or less,preferably from about 0.01 to about 2.75, more preferably from about 0.1to about 2.75, most preferably from about 0.75 to about 2.25 units per100 daltons molecular weight at a pH of from about 4 to about 12.

In general, the amino acids suitable for use in forming theproteinaceous suds stabilizers of the present invention have theformula:

wherein R and R¹ are each independently hydrogen, C₁-C₆ linear orbranched alkyl, C₁-C₆ substituted alkyl, and mixtures thereof.Non-limiting examples of suitable moieties for substitution on the C₁-C₆alkyl units include amino, hydroxy, carboxy, amido, thio, thioalkyl,phenyl, substituted phenyl, wherein said phenyl substitution is hydroxy,halogen, amino, carboxy, amido, and mixtures thereof. Furthernon-limiting examples of suitable moieties for substitution on the R andR¹ C₁-C₆ alkyl units include 3-imidazolyl, 4-imidazolyl, 2-imidazolinyl,4-imidazolinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl,1-pyrazolyl, 3-pyrazoyl, 4-pyrazoyl, 5-pyrazoyl, 1-pyrazolinyl,3-pyrazolinyl, 4-pyrazolinyl, 5-pyrazolinyl, 2-pyridinyl, 3-pyridinyl,4-pyridinyl, piperazinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, guanidino,amidino, and mixtures thereof. Preferably R¹ is hydrogen and at least10% of R units are moieties which are capable of having a positive ornegative charge at a pH of from about 4 to about 12. Each R² isindependently hydrogen, hydroxy, amino, guanidino, C₁-C₄ alkyl, orcomprises a carbon chain which can be taken together with R, R¹ any R²units to form an aromatic or non-aromatic ring having from 5 to 10carbon atoms wherein said ring may be a single ring or two fused rings,each ring being aromatic, non-aromatic, or mixtures thereof. When theamino acids according to the present invention comprise one or morerings incorporated into the amino acid backbone, then R, R¹, and one ormore R² units will provide the necessary carbon-carbon bonds toaccommodate the formation of said ring. Preferably when R is hydrogen,R¹ is not hydrogen, and vice versa; preferably at least one R² ishydrogen. The indices x and y are each independently from 0 to 2.

An example of an amino acid according to the present invention whichcontains a ring as part of the amino acid backbone is 2-aminobenzoicacid (anthranilic acid) having the formula:

wherein x is equal to 1, y is equal to 0 and R, R¹, and 2 R² units fromthe same carbon atom are taken together to form a benzene ring.

A further example of an amino acid according to the present inventionwhich contains a ring as part of the amino acid backbone is3-aminobenzoic acid having the formula:

wherein x and y are each equal to 1, R is hydrogen and R¹ and four R²units are taken together to form a benzene ring.

Non-limiting examples of amino acids suitable for use in theproteinaceous suds stabilizers of the present invention wherein at leastone x or y is not equal to 0 include 2-aminobenzoic acid, 3-aminobenzoicacid, 4-aminobenzoic acid,

anine, and

hydroxyaminobutyric acid.

The preferred amino acids suitable for use in the proteinaceous sudsstabilizers of the present invention have the formula:

wherein R and R¹ are independently hydrogen or a moiety as describeherein above preferably R¹ is hydrogen and R comprise a moiety having apositive charge at a pH of from about 4 to about 12 wherein the polymershave an average cationic charge density of 2.77 or less, preferably fromabout 0.01 to about 2.75, more preferably from about 0.1 to about 2.75,most preferably from about 0.75 to about 2.25 units per 100 daltonsmolecular weight at a pH of from about 4 to about 12.

More preferred amino acids which comprise the proteinaceous sudsstabilizers of the present invention have the formula:

wherein R hydrogen, C₁-C₆ linear or branched alkyl, C₁-C₆ substitutedalkyl, and mixtures thereof. R is preferably C₁-C₆ substituted alkylwherein preferred moieties which are substituted on said C₁-C₆ alkylunits include amino, hydroxy, carboxy, amido, thio, C₁-C₄ thioalkyl,3-imidazolyl, 4-imidazolyl, 2-imidazolinyl, 4-imidazolinyl,2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1-pyrazolyl, 3-pyrazoyl,4-pyrazoyl, 5-pyrazoyl, 1-pyrazolinyl, 3-pyrazolinyl, 4-pyrazolinyl,5-pyrazolinyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, piperazinyl,2-pyrrolidinyl, 3-pyrrolidinyl, guanidino, amidino, phenyl, substitutedphenyl, wherein said phenyl substitution is hydroxy, halogen, amino,carboxy, and amido.

An example of a more preferred amino acid according to the presentinvention is the amino acid lysine having the formula:

wherein R is a substituted C₁ alkyl moiety, said substituent is4-imidazolyl.

Non-limiting examples of preferred amino acids include alanine,arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid,glycine, histidine, isoleucine, leucine, lysine, methionine,phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine,and mixtures thereof. The aforementioned amino acids are typicallyreferred to as the “primary

amino acids”, however, the proteinaceous suds stabilizers of the presentinvention may comprise any amino acid having an R unit which togetherwith the aforementioned amino acids serves to adjust the cationic chargedensity of the proteinaceous suds stabilizers to a range from 2.77 orless, preferably from about 0.01 to about 2.75, more preferably fromabout 0.1 to about 2.75, most preferably from about 0.75 to about 2.25units per 100 daltons molecular weight at a pH of from about 4 to about12.

For example, further non-limiting examples of amino acids includehomoserine, hydroxyproline, norleucine, norvaline, ornithine,penicillamine, and phenylglycine, preferably ornithine R unitspreferably comprise moieties which are capable of a cationic or anioniccharges within the range of pH from about 4 to about 12. Non-limitingexamples of preferred amino acids having anionic R units includeglutamic acid, aspartic acid, and

carboxyglutamic acid.

For the purposes of the present invention, both optical isomers of anyamino acid having a chiral center serve equally well for inclusion intothe backbone of the peptide, polypeptide, or amino acid copolymers.Racemic mixtures of one amino acid may be suitably combined with asingle optical isomer of one or more other amino acids depending uponthe desired properties of the final proteinaceous suds stabilizer. Thesame applies to amino acids capable of forming diasteriomeric pairs, forexample, threonine.

Non-limiting examples of such stabilizers are described in PCTInternational Application Serial No. PCT/US98/24707.

Polyamino Acid Proteinaceous Suds Stabilizer

One type of suitable proteinaceous suds stabilizer according to thepresent invention is comprised entirely of the amino acids describedherein above. Said polyamino acid compounds may be naturally occurringpeptides, polypeptides, enzymes, and the like, provided that thepolymers have an average cationic charge density of 2.77 or less,preferably from about 0.01 to about 2.75, more preferably from about 0.1to about 2.75, most preferably from about 0.75 to about 2.25 units per100 daltons molecular weight at a pH of from about 4 to about 12.

An example of a polyamino acid which is suitable as a proteinaceous sudsstabilizer according to the present invention is the enzyme lysozyme.

An exception may, from time to time, occur in the case where naturallyoccurring enzymes, proteins, and peptides are chosen as proteinaceoussuds stabilizers provided that the polymers have an average cationiccharge density of 2.77 or less, preferably from about 0.01 to about2.75, more preferably from about 0.1 to about 2.75, most preferably fromabout 0.75 to about 2.25 units per 100 daltons molecular weight at a pHof from about 4 to about 12.

Another class of suitable polyamino acid compound is the syntheticpeptide having a molecular weight of at least about 1500 daltons. Inaddition, the polymers have an average cationic charge density of 2.77or less, preferably from about 0.01 to about 2.75, more preferably fromabout 0.1 to about 2.75, most preferably from about 0.75 to about 2.25units per 100 daltons molecular weight at a pH of from about 4 to about12.

An example of a polyamino acid synthetic peptide suitable for use as aproteinaceous suds stabilizer according to the present invention is thecopolymer of the amino acids lysine, alanine, glutamic acid, andtyrosine having an average molecular weight of 52,000 daltons and aratio of lys:ala:glu:tyr of approximately 5:6:2:1.

Without wishing to be limited by theory, the presence of one or morecationic amino acids, for example, histidine, ornithine, lysine and thelike, is required to insure increased suds stabilization and sudsvolume. However, the relative amount of cationic amino acid present, aswell as the average cationic charge density of the polyamino acid, arekey to the effectiveness of the resulting material. For example, polyL-lysine having a molecular weight of approximately 18,000 daltonscomprises 100% amino acids which have the capacity to possess a positivecharge in the pH range of from about 4 to about 12, with the result thatthis material is ineffective as a suds extender and as a greasy soilremoving agent.

Peptide Copolymers

Another class of materials suitable for use as proteinaceous sudsstabilizers according to the present invention are peptide copolymers.For the purposes of the present invention “peptide copolymers” aredefined as “polymeric materials with a molecular weight greater than orequal to about 1500 daltons wherein at least about 10% by weight of saidpolymeric material comprises one or more amino acids”.

Peptide copolymers suitable for use as proteinaceous suds stabilizersmay include segments of polyethylene oxide which are linked to segmentsof peptide or polypeptide to form a material which has increased sudsretention as well as formulatability.

Nonlimiting examples of amino acid copolymer classes include thefollowing.

Polyalkyleneimine copolymers comprise random segments ofpolyalkyleneimine, preferably polyethyleneimine, together with segmentsof amino acid residues. For example, tetraethylenepentamine is reactedtogether with polyglutamic acid and polyalanine to form a copolymerhaving the formula:

wherein m is equal to 3, n is equal to 0, i is equal to 3, j is equal to5, x is equal to 3, y is equal to 4, and z is equal to 7.

However, the formulator may substitute other polyamines forpolyalkyleneimines, for example, polyvinyl amines, or other suitablepolyamine which provides for a source of cationic charge at a pH of from4 to about 12 and which results in a copolymer having an averagecationic charge density of 2.77 or less, preferably from about 0.01 toabout 2.75, more preferably from about 0.1 to about 2.75, mostpreferably from about 0.75 to about 2.25 units per 100 daltons molecularweight at a pH of from about 4 to about 12.

The formulator may combine non-amine polymers with protonatable as wellas non-protonatable amino acids. For example, a carboxylate-containinghomo-polymer may be reacted with one or more amino acids, for example,histidine and glycine, to form an amino acid containing amido copolymerhaving the formula:

wherein said copolymer has a molecular weight of at least 1500 daltonsand a ratio of x:y:z of approximately 2:3:6.

Zwitterionic Polymers

The polymeric suds stabilizer/soil release agents of the presentinvention are homopolymers or copolymers wherein the monomers whichcomprise said homopolymers or copolymers contain a moiety capable ofbeing protonated at a pH of from about 4 to about 12, or a moietycapable of being de-protonated at a pH of from about 4 to about 12, of amixture of both types of moieties.

A Preferred class of zwitterionic polymer suitable for use as a sudsvolume and suds duration enhancer has the formula:

wherein R is C₁-C₁₂ linear alkylene, C₁-C₁₂ branched alkylene, andmixtures thereof; preferably C₁-C₄ linear alkylene, C₃-C₄ branchedalkylene; more preferably methylene and 1,2-propylene. The index x isfrom 0 to 6; y is 0 or 1; z is 0 or 1.

The index n has the value such that the zwitterionic polymers of thepresent invention have an average molecular weight of from about 1,000to about 2,000,000 preferably from about 5,000 to about 1,000,000, morepreferably from about 10,000 to about 750,000, more preferably fromabout 20,000 to about 500,000, even more preferably from about 35,000 toabout 300,000 daltons. The molecular weight of the polymeric sudsboosters, can be determined via conventional gel permeationchromatography.

Non-limiting examples of such stabilizers are disclosed by PCTInternational Application Serial No. PCT/US98/24699.

Anionic Units

R¹ is a unit capable of having a negative charge at a pH of from about 4to about 12. Preferred R¹ has the formula:

-(L)_(i)-(S)_(j)—R³

wherein L is a linking unit independently selected from the following:

and mixtures thereof, wherein R′ is independently hydrogen, C₁-C₄ alkyl,and mixtures thereof; preferably hydrogen or alternatively R′ and S canform a heterocycle of 4 to 7 carbon atoms, optionally containing otherhetero atoms and optionally substituted. Preferably the linking group Lcan be introduced into the molecule as part of the original monomerbackbone, for example, a polymer having L units of the formula:

can suitably have this moiety introduced into the polymer via acarboxylate containing monomer, for example, a monomer having thegeneral formula:

When the index i is 0, L is absent.

For anionic units S is a “spacing unit” wherein each S unit isindependently selected from C₁-C₁₂ linear alkylene, C₁-C₁₂ branchedalkylene, C₃-C₁₂ linear alkenylene, C₃-C₁₂ branched alkenylene, C₃-C₁₂hydroxyalkylene, C₄-C₁₂ dihydroxyalkylene, C₆-C₁₀ arylene, C₈-C₁₂dialkylarylene, —(R⁵O)_(k)R⁵—, —(R⁵O)_(k)R⁶(OR⁵)_(k)—, —CH₂CH(OR⁷)CH₂—,and mixtures thereof; wherein R⁵ is C₂-C₄ linear alkylene, C₃-C₄branched alkylene, and mixtures thereof, preferably ethylene,1,2-propylene, and mixtures thereof, more preferably ethylene; R⁶ isC₂-C₁₂ linear alkylene, and mixtures thereof, preferably ethylene; R⁷ ishydrogen, C₁-C₄ alkyl, and mixtures thereof, preferably hydrogen. Theindex k is from 1 to about 20.

Preferably S is C₁-C₁₂ linear alkylene, —(R⁵O)_(k)R⁵—, and mixturesthereof. When S is a —(R⁵O)_(k)R⁵— unit, said units may be suitablyformed by the addition an alkyleneoxy producing reactant (e.g. ethyleneoxide, epichlorohydrin) or by addition of a suitable polyethyleneglycol.More preferably S is C₂-C₄ linear alkylene. When the index j is 0 the Sunit is absent.

R³ is independently selected from hydrogen, —CO₂M, —SO₃M, —OSO₃M,—CH₂P(O)(OM)₂, —OP(O)(OM)₂, units having the formula:

—CR⁸R⁹R¹⁰

wherein each R⁸, R⁹, and R¹⁰ is independently selected from the groupconsisting of hydrogen, —(CH₂)_(m)R¹¹, and mixtures thereof, wherein R¹¹is —CO₂H, —SO₃M, —OSO₃M, —CH(CO₂H)CH₂CO₂H, —CH₂P(O)(OH)₂, —OP(O)(OH)₂,and mixtures thereof, preferably —CO₂H, —CH(CO₂H)CH₂CO₂H, and mixturesthereof, more preferably —CO₂H; provided that one R⁸, R⁹, or R¹⁰ is nota hydrogen atom, preferably two R⁸, R⁹, or R¹⁰ units are hydrogen. M ishydrogen or a salt forming cation, preferably hydrogen. The index m hasthe value from 0 to 10.

Cationic Units

R² is a unit capable of having a positive charge at a pH of from about 4to about 12. Preferred R² has the formula:

-(L¹)_(i′)-(S)_(j′)—R⁴

wherein L¹ is a linking unit independently selected from the following:

and mixtures thereof; wherein R′ is independently hydrogen, C₁-C₄ alkyl,and mixtures thereof; preferably hydrogen or alternatively R′ and S canform a heterocycle of 4 to 7 carbon atoms, optionally containing otherhetero atoms and optionally substituted. Preferably L¹ has the formula:

When the index i′ is equal to 0, L¹ is absent.

For cationic units S is a “spacing unit” wherein each S unit isindependently selected from C₁-C₁₂ linear alkylene, C₁-C₁₂ branchedalkylene, C₃-C₁₂ linear alkenylene, C₃-C₁₂ branched alkenylene, C₃-C₁₂hydroxyalkylene, C₄-C₁₂ dihydroxyalkylene, C₆-C₁₀ arylene, C₈-C₁₂dialkylarylene, —(R⁵O)_(k)R⁵—, —(R⁵O)_(k)R⁶(OR⁵)_(k)—, —CH₂CH(OR⁷)CH₂—,and mixtures thereof; wherein R⁵ is C₂-C₄ linear alkylene, C₃-C₄branched alkylene, and mixtures thereof, preferably ethylene,1,2-propylene, and mixtures thereof, more preferably ethylene; R⁶ isC₂-C₁₂ linear alkylene, and mixtures thereof, preferably ethylene; R⁷ ishydrogen, C₁-C₄ alkyl, and mixtures thereof, preferably hydrogen. Theindex k is from 1 to about 20.

Preferably S is C₁-C₁₂ linear alkylene, and mixtures thereof. PreferablyS is C₂-C₄ linear alkylene. When the index j′ is 0 the S unit is absent.

R⁴ is independently selected from amino, alkylamino carboxamide,3-imidazolyl, 4-imidazolyl, 2-imidazolinyl, 4-imidazolinyl,2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1-pyrazolyl, 3-pyrazoyl,4-pyrazoyl, 5-pyrazoyl, 1-pyrazolinyl, 3-pyrazolinyl, 4-pyrazolinyl,5-pyrazolinyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, piperazinyl,2-pyrrolidinyl, 3-pyrrolidinyl, guanidino, amidino, and mixturesthereof, preferably dialkylamino having the formula:

—N(R¹¹)₂

wherein each R¹¹ is independently hydrogen, C₁-C₄ alkyl, and mixturesthereof, preferably hydrogen or methyl or alternatively the two R¹¹ canform a heterocycle of 4 to 8 carbon atoms, optionally containing otherhetero atoms and optionally substituted.

An example of a preferred zwitterionic polymer according to the presentinvention has the formula:

wherein X is C₆, n has a value such that the average molecular weight isfrom about 1,000 to about 2,000,000.

Further preferred zwitterionic polymers according to the presentinvention are polymers comprising monomers wherein each monomer has onlycationic units or anionic units, said polymers have the formula:

wherein R, R¹, x, y, and z are the same as defined herein above; n¹+n²=nsuch that n has a value wherein the resulting zwitterionic polymer has amolecular weight of form about 1,000 to about 2,000,000 daltons,provided that the resulting zwitterionic polymer having an averagecationic charge density of 2.77 or less, preferably from about 0.01 toabout 2.75, more preferably from about 0.1 to about 2.75, mostpreferably from about 0.75 to about 2.25 units per 100 daltons molecularweight at a pH of from about 4 to about 12.

An example of a polymer having monomers with only an anionic unit or acationic unit has the formula:

wherein the sum of n¹ and n² provide a polymer with an average molecularweight of from about 1,000 to about 2,000,000 daltons.

Another preferred zwitterionic polymer according to the presentinvention are polymers which have limited crosslinking, said polymershaving the formula:

wherein R, R¹, L¹, S, j′, x, y, and z are the same as defined hereinabove; n′ is equal to n″, and the value n′+n″ is less than or equal to5% of the value of n¹+n²=n; n provides a polymer with an averagemolecular weight of from about 1,000 to about 2,000,000 daltons. R¹² isnitrogen, C₁-C₁₂ linear alkylene amino alkylene having the formula:

—R¹³—N—R¹³—

L¹, and mixtures thereof, wherein each R¹³ is independently L¹ orethylene.

The zwitterionic polymers of the present invention may comprise anycombination of monomer units, for example, several different monomershaving various R¹ and R² groups can be combined to form a suitable sudsstabilizer. Alternatively the same R¹ unit may be used with a selectionof different R² units and vice versa.

Cationic Charge Density

For the purposes of the present invention the term “cationic chargedensity” is defined as “the total number of units that are protonated ata specific pH per 100 daltons mass of polymer, or otherwise stated, thetotal number of charges divided by the dalton molecular weight of themonomer unit or polymer.”

For illustrative purposes only, a polypeptide comprising 10 units of theamino acid lysine has a molecular weight of approximately 1028 daltons,wherein there are 11 —NH₂ units. If at a specific pH within the range offrom about 4 to about 12, 2 of the —NH₂ units are protonated in the formof —NH₃ ⁺, then the cationic charge density is 2 cationic chargeunits÷by 1028 daltons molecular weight=approximately 0.2 units ofcationic charge per 100 daltons molecular weight. This would, therefore,have sufficient cationic charge to suffice the cationic charge densityof the present invention, but insufficient molecular weight to be asuitable suds enhancer.

Polymers have been shown to be effective for delivering sudsing benefitsin a hand dishwashing context, provided the polymer contains a cationicmoiety, either permanent via a quaternary nitrogen or temporary viaprotonation. Without being limited by theory, it is believed that thecationic charge must be sufficient to attract the polymer to negativelycharged soils but not so large as to cause negative interactions withavailable anionic surfactants.

The cationic charge density may be determined as follows, where thecationic charge density is defined as the amount of cationic charge on agiven polymer, either by permanent cationic groups or via protonatedgroups, as a weight percent of the total polymer at the desired wash pH.For example, with the terpolymer, DMAM/hydroxyethylacrylate(HEA)/acrylic acid (AA) where the ratio of monomers is 1 mole of DMAMfor 3 moles of HEA for 0.33 moles of AA, we have experimentallydetermined the pKa, see hereinafter as to how pKa is measured, of thispolymer to be 8.2. Thus, if the wash pH is 8.2, then half of theavailable nitrogens will be protonated (and count as cationic) and theother half will not be protonated (and not be counted in the “cationiccharge density”). Thus, since the Nitrogen has a molecular weight ofapproximately 14 grams/mole, the DMAM monomer has a molecular weight ofapproximately 157 grams/mole, the HEA monomer has a molecular weight ofapproximately 116 grams/mole, and the AA monomer has a molecular weightof approximately 72 grams/mole, the cationic charge density can becalculated as follows:

Cationic Charge Density=(14/157+116+116+116+72)*50%=0.0132 or 1.32%.

Thus, 1.32% of the polymer contains cationic charges. Otherwise stated,the cationic charge density is 1.32 per 100 daltons molecular weight.

As another example, one could make a copolymer of DMAM withhydroxyethylacrylate (HEA), where the ratio of monomers is 1 mole ofDMAM for 3 moles of HEA. The DMAM monomer has a molecular weight ofapproximately 157 and the HEA monomer has a molecular weight of 116grams/mole. In this case the pKa has been measured to be 7.6. Thus, ifthe wash pH is 5.0, all of the available nitrogens will be protonated.The cationic charge density is then calculated:

Cationic Charge Density=14/(157+116+116+116)*100%=0.0277, or 2.77%.

Thus, the cationic charge density is 2.77 per 100 daltons molecularweight. Notice that in this example, the minimum repeating unit isconsidered 1 DMAM monomer plus 3 HEA monomers.

Alternatively, the cationic charge density can be determined as follows:where the cationic charge density is defined as the total number ofcharges divided by the dalton molecular weight of the polymer at thedesired wash pH. It can be calculated from the following equation

${{Cationic}\mspace{14mu} {Charge}\mspace{14mu} {Density}} = \frac{\sum\limits_{i}{n_{i}f_{i}C_{i}}}{\sum\limits_{j}m_{j}}$

where n_(i) is the number of charged unit. f_(i) is the fraction of unitbeing charged. In the case of protonated species (AH⁺), f_(i) can becalculated from the measured pH and pKa.

$f_{({{AH} +})} = \frac{10^{{pKa} - {p\; H}}}{1 + 10^{{pKa} - {p\; H}}}$

In the case of deprotonated anionic species (A⁻)

$f_{({A -})} = \frac{10^{{p\; H} - {pKa}}}{1 + 10^{{p\; H} - {pKa}}}$

C_(i) is the charge of the unit, m_(j) is the dalton molecular weight ofthe individual monomer units.

For example, with polyDMAM, we have experimentally determined the pKa,see hereinafter as to how pKa is measured, of this polymer to be 7.7.Thus, if the wash pH is 7.7, then half of the available nitrogens willbe protonated (and count as cationic) f_((AH+))=0.5 and the other halfwill not be protonated (and not be counted in the “cationic chargedensity”). Thus, since the DMAM monomer has a molecular weight ofapproximately 157 grams/mole, the cationic charge density can becalculated:

Cationic Charge Density=(1*0.5/157)=0.00318 or 0.318%.

Thus, at the wash pH of 7.7, polyDMAM has a cationic charge density of0.318 charge per 100 dalton molecular weight. As another example, onecould make a copolymer of DMAM with DMA, where the ratio of monomers is1 mole of DMAM for 3 moles of DMA. The DMA monomer has a molecularweight of 99 grams/mole. In this case the pKa has been measured to be7.6. Thus, if the wash pH is 5.0, all of the available nitrogens will beprotonated. The cationic charge density is then calculated:

Cationic Charge Density=1/(157+99+99+99)=0.0022, or 0.22%.

At the wash pH of 5.0, a copolymer of DMAM with DMA has a charge densityof 0.22 charge per 100 dalton molecular weight. Notice that in thisexample, the minimum repeating unit is considered 1 DMAM monomer plus 3DMA monomers.

A key aspect of this calculation is the pKa measurement for anyprotonatable species which will result in a cationic charge on theheteroatom. Since the pKa is dependent on the polymer structure andvarious monomers present, this must be measure to determine thepercentage of protonatable sites to count as a function of the desiredwash pH. This is an easy exercise for one skilled in the art. Based onthis calculation, the percent of cationic charge is independent ofpolymer molecular weight.

The pKa of a polymeric suds booster is determined in the followingmanner Make at least 50 mls of a 5% polymer solution, such as a polymerprepared according to any of Examples 1 to 5 as described hereinafter,in ultra pure water (i.e. no added salt). At 25° C., take initial pH ofthe 5% polymer solution with a pH meter and record when a steady readingis achieved. Maintain temperature throughout the test at 25° C. with awater bath and stir continuously. Raise pH of 50 mls of the aqueouspolymer solution to 12 using NaOH (1N, 12.5M). Titrate 5 mls of 0.1N HClinto the polymer solution. Record pH when steady reading is achieved.Repeat steps 4 and 5 until pH is below 3. The pKa was determined from aplot of pH vs. volume of titrant using the standard procedure asdisclosed in Quantitative Chemical Analysis, Daniel C. Harris, W.H.Freeman & Chapman, San Francisco, USA 1982.

It has been surprisingly found that when a polymeric suds booster of thepresent invention is at its optimum charge density, then reducing themolecular weight of the polymeric suds booster increases sudsingperformance even in the presence of composite and/or greasy soils.Accordingly, then the polymeric suds booster is at its optimum chargedensity, the molecular weight of the polymeric suds booster, asdetermined in the manner described hereinbefore, is preferably in therange of from about 1,000 to about 2,000,000, more preferably from about5,000 to about 500,000, even more preferably from about 10,000 to about100,000, most preferably from about 20,000 to about 50,000 daltons.

The liquid detergent compositions according to the present inventioncomprise at least an effective amount of one or more polymeric sudsstabilizers described herein, preferably from about 0.01% to about 10%,more preferably from about 0.001% to about 5%, most preferably fromabout 0.1% to about 2% by weight, of said composition. What is meantherein by “an effective amount of polymeric suds stabilizer” is that thesuds produced by the presently described compositions are sustained foran increased amount of time relative to a composition which does notcomprise a polymeric suds stabilizer described herein.

For other uses of these block polymers, e.g., personal care (such ashand/body wash, soap, shampoo, shaving cream, shaving gel,diphiliatories), oil field foam, fire fighting foam, agrochemical foam,hard surface (e.g., bathroom tile) foam cleaner, shower rinse, andcoagulants/retention aids for titanium dioxide used in paper production.The effective amounts for each use are the amounts which result in animprovement in the desired property in comparison with a compositionlacking the polymer.

Hand Dishwashing Compositions and Methods of Use Detersive Surfactantsfor Hand Dishwashing

Anionic Surfactants—The anionic surfactants useful in the presentinvention are preferably selected from the group consisting of, linearalkylbenzene sulfonate, alpha olefin sulfonate, paraffin sulfonates,alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfate, alkylsulfonates, alkyl alkoxy carboxylate, alkyl alkoxylated sulfates,sarcosinates, taurinates, and mixtures thereof. An effective amount,typically from about 0.5% to about 90%, preferably about 5% to about60%, more preferably from about 10 to about 30%, by weight of anionicdetersive surfactant can be used in the present invention.

Alkyl sulfate surfactants are another type of anionic surfactant ofimportance for use herein. In addition to providing excellent overallcleaning ability when used in combination with polyhydroxy fatty acidamides (see below), including good grease/oil cleaning over a wide rangeof temperatures, wash concentrations, and wash times, dissolution ofalkyl sulfates can be obtained, as well as improved formulability inliquid detergent formulations are water soluble salts or acids of theformula ROSO₃M wherein R preferably is a C₁₀-C₂₄ hydrocarbyl, preferablyan alkyl or hydroxyalkyl having a C₁₀-C₂₀ alkyl component, morepreferably a C₁₂-C₁₈ alkyl or hydroxyalkyl, and M is H or a cation,e.g., an alkali (Group IA) metal cation (e.g., sodium, potassium,lithium), substituted or unsubstituted ammonium cations such as methyl-,dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g.,tetramethyl-ammonium and dimethyl piperidinium, and cations derived fromalkanolamines such as ethanolamine, diethanolamine, triethanolamine, andmixtures thereof, and the like. Typically, alkyl chains of C₁₂₋₁₆ arepreferred for lower wash temperatures (e.g., below about 50° C.) andC₁₆₋₁₈ alkyl chains are preferred for higher wash temperatures (e.g.,above about 50° C.).

Alkyl alkoxylated sulfate surfactants are another category of usefulanionic surfactant. These surfactants are water soluble salts or acidstypically of the formula RO(A)_(m)SO₃M wherein R is an unsubstitutedC₁₀-C₂₄ alkyl or hydroxyalkyl group having a C₁₀-C₂₄ alkyl component,preferably a C₁₂-C₂₀ alkyl or hydroxyalkyl, more preferably C₁₂-C₁₈alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater thanzero, typically between about 0.5 and about 6, more preferably betweenabout 0.5 and about 3, and M is H or a cation which can be, for example,a metal cation (e.g., sodium, potassium, lithium, etc.), ammonium orsubstituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkylpropoxylated sulfates are contemplated herein. Specific examples ofsubstituted ammonium cations include methyl-, dimethyl-,trimethyl-ammonium and quaternary ammonium cations, such astetramethyl-ammonium, dimethyl piperidinium and cations derived fromalkanolamines, e.g. monoethanolamine, diethanolamine, andtriethanolamine, and mixtures thereof. Exemplary surfactants are C₁₂-C₁₈alkyl polyethoxylate (1.0) sulfate, C₁₂-C₁₈ alkyl polyethoxylate (2.25)sulfate, C₁₂-C₁₈ alkyl polyethoxylate (3.0) sulfate, and C₁₂-C₁₈ alkylpolyethoxylate (4.0) sulfate wherein M is conveniently selected fromsodium and potassium. Surfactants for use herein can be made fromnatural or synthetic alcohol feedstocks. Chain lengths represent averagehydrocarbon distributions, including branching.

Examples of suitable anionic surfactants are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch). Avariety of such surfactants are also generally disclosed in U.S. Pat.No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23,line 58 through Column 29, line 23.

Secondary Surfactants—Secondary detersive surfactant can be selectedfrom the group consisting of nonionics, cationics, ampholytics,zwitterionics, and mixtures thereof. By selecting the type and amount ofdetersive surfactant, along with other adjunct ingredients disclosedherein, the present detergent compositions can be formulated to be usedin the context of laundry cleaning or in other different cleaningapplications, particularly including dishwashing. The particularsurfactants used can therefore vary widely depending upon the particularend-use envisioned. Suitable secondary surfactants are described below.Examples of suitable nonionic, cationic amphoteric and zwitterionicsurfactants are given in “Surface Active Agents and Detergents” (Vol. Iand II by Schwartz, Perry and Berch).

Nonionic Detergent Surfactants—Suitable nonionic detergent surfactantsare generally disclosed in U.S. Pat. No. 3,929,678, Laughlin et al.,issued Dec. 30, 1975, at column 13, line 14 through column 16, line 6,incorporated herein by reference. Exemplary, non-limiting classes ofuseful nonionic surfactants include: amine oxides, alkyl ethoxylate,alkanoyl glucose amide, alkyl betaines, sulfobetaine and mixturesthereof.

Amine oxides are semi-polar nonionic surfactants and includewater-soluble amine oxides containing one alkyl moiety of from about 10to about 18 carbon atoms and 2 moieties selected from the groupconsisting of alkyl groups and hydroxyalkyl groups containing from about1 to about 3 carbon atoms; water-soluble phosphine oxides containing onealkyl moiety of from about 10 to about 18 carbon atoms and 2 moietiesselected from the group consisting of alkyl groups and hydroxyalkylgroups containing from about 1 to about 3 carbon atoms; andwater-soluble sulfoxides containing one alkyl moiety of from about 10 toabout 18 carbon atoms and a moiety selected from the group consisting ofalkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxidesurfactants having the formula

wherein R³ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixturesthereof containing from about 8 to about 22 carbon atoms; R⁴ is analkylene or hydroxyalkylene group containing from about 2 to about 3carbon atoms or mixtures thereof; x is from 0 to about 3; and each R⁵ isan alkyl or hydroxyalkyl group containing from about 1 to about 3 carbonatoms or a polyethylene oxide group containing from about 1 to about 3ethylene oxide groups. The R⁵ groups can be attached to each other,e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include C₁₀-C₁₈ alkyldimethyl amine oxides and C₈-C₁₂ alkoxy ethyl dihydroxy ethyl amineoxides. Preferably the amine oxide is present in the composition in aneffective amount, more preferably from about 0.1% to about 20%, evenmore preferably about 0.1% to about 15%, even more preferably still fromabout 0.5% to about 10%, by weight.

The polyethylene, polypropylene, and polybutylene oxide condensates ofalkyl phenols. In general, the polyethylene oxide condensates arepreferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from about 6 to about 12 carbonatoms in either a straight chain or branched chain configuration withthe alkylene oxide. In a preferred embodiment, the ethylene oxide ispresent in an amount equal to from about 5 to about 25 moles of ethyleneoxide per mole of alkyl phenol. Commercially available nonionicsurfactants of this type include Igepal® CO-630, marketed by the GAFCorporation; and Triton® X-45, X-114, X-100, and X-102, all marketed bythe Rohm & Haas Company. These compounds are commonly referred to asalkyl phenol alkoxylates, (e.g., alkyl phenol ethoxylates).

The condensation products of aliphatic alcohols with from about 1 toabout 25 moles of ethylene oxide. The alkyl chain of the aliphaticalcohol can either be straight or branched, primary or secondary, andgenerally contains from about 8 to about 22 carbon atoms. Particularlypreferred are the condensation products of alcohols having an alkylgroup containing from about 10 to about 20 carbon atoms with from about2 to about 18 moles of ethylene oxide per mole of alcohol. Examples ofcommercially available nonionic surfactants of this type includeTergitol® 15-S-9 (the condensation product of C₁₁-C₁₅ linear secondaryalcohol with 9 moles ethylene oxide), Tergitol® 24-L-6 NMW (thecondensation product of C₁₂-C₁₄ primary alcohol with 6 moles ethyleneoxide with a narrow molecular weight distribution), both marketed byUnion Carbide Corporation; Neodol® 45-9 (the condensation product ofC₁₄-C₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol 23-6.5(the condensation product of C₁₂-C₁₃ linear alcohol with 6.5 moles ofethylene oxide), Neodol® 45-7 (the condensation product of C₁₄-C₁₅linear alcohol with 7 moles of ethylene oxide), Neodol® 45-4 (thecondensation product of C₁₄-C₁₅ linear alcohol with 4 moles of ethyleneoxide), marketed by Shell Chemical Company, and Kyro® EOB (thecondensation product of C₁₃-C₁₅ alcohol with 9 moles ethylene oxide),marketed by The Procter & Gamble Company. Other commercially availablenonionic surfactants include Dobanol 91-8® marketed by Shell ChemicalCo. and Genapol UD-080® marketed by Hoechst. This category of nonionicsurfactant is referred to generally as “alkyl ethoxylates.”

The preferred alkylpolyglycosides have the formula

R²O(C_(n)H_(2n)O)_(t)(glycosyl)_(x)

wherein R² is selected from the group consisting of alkyl, alkyl-phenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from about 10 to about 18, preferably from about 12to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 toabout 10, preferably 0; and x is from about 1.3 to about 10, preferablyfrom about 1.3 to about 3, most preferably from about 1.3 to about 2.7.The glycosyl is preferably derived from glucose. To prepare thesecompounds, the alcohol or alkylpolyethoxy alcohol is formed first andthen reacted with glucose, or a source of glucose, to form the glucoside(attachment at the 1-position). The additional glycosyl units can thenbe attached between their 1-position and the preceding glycosyl units2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.

Fatty acid amide surfactants having the formula:

wherein R⁶ is an alkyl group containing from about 7 to about 21(preferably from about 9 to about 17) carbon atoms and each R⁷ isselected from the group consisting of hydrogen, C₁-C₄ alkyl, C₁-C₄hydroxyalkyl, and —(C²H₄O)_(x)H where x varies from about 1 to about 3.

Preferred amides are C₈-C₂₀ ammonia amides, monoethanolamides,diethanolamides, and isopropanolamides.

Preferably the nonionic surfactant, when present in the composition, ispresent in an effective amount, more preferably from about 0.1% to about20%, even more preferably about 0.1% to about 15%, even more preferablystill from about 0.5% to about 10%, by weight.

Polyhydroxy Fatty Acid Amide Surfactant—The detergent compositionshereof may also contain an effective amount of polyhydroxy fatty acidamide surfactant. By “effective amount” is meant that the formulator ofthe composition can select an amount of polyhydroxy fatty acid amide tobe incorporated into the compositions that will improve the cleaningperformance of the detergent composition. In general, for conventionallevels, the incorporation of about 1%, by weight, polyhydroxy fatty acidamide will enhance cleaning performance.

The detergent compositions herein will typically comprise about 1%weight basis, polyhydroxy fatty acid amide surfactant, preferably fromabout 3% to about 30%, of the polyhydroxy fatty acid amide. Thepolyhydroxy fatty acid amide surfactant component comprises compounds ofthe structural formula:

wherein: R¹ is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl,or a mixture thereof, preferably C₁-C₄ alkyl, more preferably C₁ or C₂alkyl, most preferably C₁ alkyl (i.e., methyl); and R² is a C₅-C₃₁hydrocarbyl, preferably straight chain C₇-C₁₉ alkyl or alkenyl, morepreferably straight chain C₉-C₁₇ alkyl or alkenyl, most preferablystraight chain C₁₁-C₁₅ alkyl or alkenyl, or mixtures thereof; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z preferably will bederived from a reducing sugar in a reductive amination reaction; morepreferably Z will be a glycityl. Suitable reducing sugars includeglucose, fructose, maltose, lactose, galactose, mannose, and xylose. Asraw materials, high dextrose corn syrup, high fructose corn syrup, andhigh maltose corn syrup can be utilized as well as the individual sugarslisted above. These corn syrups may yield a mix of sugar components forZ. It should be understood that it is by no means intended to excludeother suitable raw materials. Z preferably will be selected from thegroup consisting of —CH₂—(CHOH)_(n)—CH₂OH,—CH(CH₂OH)—(CHOH)_(n-1)—CH₂OH, —CH₂—(CHOH)₂(CHOR′)(CHOH)—CH₂OH, andalkoxylated derivatives thereof, where n is an integer from 3 to 5,inclusive, and R′ is H or a cyclic or aliphatic monosaccharide. Mostpreferred are glycityls wherein n is 4, particularly —CH₂—(CHOH)₄—CH₂OH.

R′ can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl,N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.

R²—CO—N< can be, for example, cocamide, stearamide, oleamide, lauramide,myristamide, capricamide, palmitamide, tallowamide, etc.

Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl,1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl,1-deoxymaltotriotityl, etc.

Methods for making polyhydroxy fatty acid amides are known in the art.In general, they can be made by reacting an alkyl amine with a reducingsugar in a reductive amination reaction to form a corresponding N-alkylpolyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with afatty aliphatic ester or triglyceride in a condensation/amidation stepto form the N-alkyl, N-polyhydroxy fatty acid amide product. Processesfor making compositions containing polyhydroxy fatty acid amides aredisclosed, for example, in G.B. Patent Specification 809,060, publishedFeb. 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Pat. No. 2,965,576,issued Dec. 20, 1960 to E. R. Wilson, and U.S. Pat. No. 2,703,798,Anthony M. Schwartz, issued Mar. 8, 1955, and U.S. Pat. No. 1,985,424,issued Dec. 25, 1934 to Piggott, each of which is incorporated herein byreference.

Diamines

The preferred liquid detergent compositions of the present inventionfurther comprise one or more diamines, preferably an amount of diaminesuch that the ratio of anionic surfactant present to the diamine is fromabout 40:1 to about 2:1. Said diamines provide for increased removal ofgrease and greasy food material while maintaining suitable levels ofsuds.

The diamines suitable for use in the compositions of the presentinvention have the formula:

-   -   wherein each R²⁰ is independently selected from the group        consisting of hydrogen, C₁-C₄ linear or branched alkyl,        alkyleneoxy having the formula:

—(R²¹O)_(y)R²²

-   -   wherein R²¹ is C₂-C₄ linear or branched alkylene, and mixtures        thereof; R²² is hydrogen, C₁-C₄ alkyl, and mixtures thereof; y        is from 1 to about 10; X is a unit selected from:    -   i) C₃-C₁₀ linear alkylene, C₃-C₁₀ branched alkylene, C₃-C₁₀        cyclic alkylene, C₃-C₁₀ branched cyclic alkylene, an        alkyleneoxyalkylene having the formula:

(R²¹O)_(y)R²¹

-   -    wherein R²¹ and y are the same as defined herein above;    -   ii) C₃-C₁₀ linear, C₃-C₁₀ branched linear, C₃-C₁₀ cyclic, C₃-C₁₀        branched cyclic alkylene, C₆-C₁₀ arylene, wherein said unit        comprises one or more electron donating or electron withdrawing        moieties which provide said diamine with a pK_(a) greater than        about 8; and    -   iii) mixtures of (i) and (ii)        provided said diamine has a pK_(a) of at least about 8.

The preferred diamines of the present invention have a pK₁ and pK₂ whichare each in the range of from about 8 to about 11.5, preferably in therange of from about 8.4 to about 11, more preferably from about 8.6 toabout 10.75. For the purposes of the present invention the term “pK_(a)”stands equally well for the terms “pK₁” and “pK₂” either separately orcollectively. The term pK_(a) as used herein throughout the presentspecification in the same manner as used by those of ordinary skill inthe art. pK_(a) values are readily obtained from standard literaturesources, for example, “Critical Stability Constants: Volume 2, Amines”by Smith and Martel, Plenum Press, N.Y. and London, (1975).

As an applied definition herein, the pK_(a) values of the diamines arespecified as being measured in an aqueous solution at 25° C. having anionic strength of from about 0.1 to about 0.5 M. As used herein, thepK_(a) is an equilibrium constant dependent upon temperature and ionicstrength, therefore, value reported by literature references, notmeasured in the above described manner, may not be within full agreementwith the values and ranges which comprise the present invention. Toeliminate ambiguity, the relevant conditions and/or references used forpK_(a)'s of this invention are as defined herein or in “CriticalStability Constants: Volume 2, Amines”. One typical method ofmeasurement is the potentiometric titration of the acid with sodiumhydroxide and determination of the pK_(a) by suitable methods asdescribed and referenced in “The Chemist's Ready Reference Handbook” byShugar and Dean, McGraw Hill, NY, 1990.

Preferred diamines for performance and supply considerations are 1,3-bis(methylamino)cyclohexane, 1,3-diaminopropane (pK₁=10.5; pK₂=8.8),1,6-diaminohexane (pK₁=11; pK₂=10), 1,3-diaminopentane (Dytek EP)(pK₁=10.5; pK₂=8.9), 2-methyl 1,5-diaminopentane (Dytek A) (pK₁=11.2;pK₂=10.0). Other preferred materials are the primary/primary diamineshaving alkylene spacers ranging from C₄-C₈. In general, primary diaminesare preferred over secondary and tertiary diamines.

The following are non-limiting examples of diamines suitable for use inthe present invention.

1-N,N-dimethylamino-3-aminopropane having the formula:

1,6-diaminohexane having the formula:

1,3-diaminopropane having the formula:

2-methyl-1,5-diaminopentane having the formula:

1,3-diaminopentane, available under the tradename Dytek EP, having theformula:

1,3-diaminobutane having the formula:

Jeffamine EDR 148, a diamine having an alkyleneoxy backbone, having theformula:

3-methyl-3-aminoethyl-5-dimethyl-1-aminocyclohexane (isophorone diamine)having the formula:

and1,3-bis(methylamino)cyclohexane having the formula:

Adjunct Ingredients for Hand Dishwashing

Builder—The compositions according to the present invention may furthercomprise a builder system. Any conventional builder system is suitablefor use herein including aluminosilicate materials, silicates,polycarboxylates and fatty acids, materials such as ethylene-diaminetetraacetate, metal ion sequestrants such as aminopolyphosphonates,particularly ethylenediamine tetramethylene phosphonic acid anddiethylene triamine pentamethylene-phosphonic acid. Though lesspreferred for obvious environmental reasons, phosphate builders can alsobe used herein.

Suitable polycarboxylates builders for use herein include citric acid,preferably in the form of a water-soluble salt, derivatives of succinicacid of the formula R—CH(COOH)CH₂(COOH) wherein R is C10-20 alkyl oralkenyl, preferably C12-16, or wherein R can be substituted withhydroxyl, sulfo sulfoxyl or sulfone substituents. Specific examplesinclude lauryl succinate, myristyl succinate, palmityl succinate2-dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders arepreferably used in the form of their water-soluble salts, includingsodium, potassium, ammonium and alkanolammonium salts.

Other suitable polycarboxylates are oxodisuccinates and mixtures oftartrate monosuccinic and tartrate disuccinic acid such as described inU.S. Pat. No. 4,663,071.

Especially for the liquid execution herein, suitable fatty acid buildersfor use herein are saturated or unsaturated C10-18 fatty acids, as wellas the corresponding soaps. Preferred saturated species have from 12 to16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acidis oleic acid. Other preferred builder system for liquid compositions isbased on dodecenyl succinic acid and citric acid.

Detergency builder salts are normally included in amounts of from 3% to50% by weight of the composition preferably from 5% to 30% and mostusually from 5% to 25% by weight.

Optional Detergent Ingredients for Hand Dishwashing

Enzymes—Detergent compositions of the present invention may furthercomprise one or more enzymes which provide cleaning performancebenefits. Said enzymes include enzymes selected from cellulases,hemicellulases, peroxidases, proteases, gluco-amylases, amylases,lipases, cutinases, pectinases, xylanases, reductases, oxidases,phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,pentosanases, malanases, B-glucanases, arabinosidases or mixturesthereof. A preferred combination is a detergent composition having acocktail of conventional applicable enzymes like protease, amylase,lipase, cutinase and/or cellulase. Enzymes when present in thecompositions, at from about 0.0001% to about 5% of active enzyme byweight of the detergent composition.

Proteolytic Enzyme—The proteolytic enzyme can be of animal, vegetable ormicroorganism (preferred) origin. The proteases for use in the detergentcompositions herein include (but are not limited to) trypsin,subtilisin, chymotrypsin and elastase-type proteases. Preferred for useherein are subtilisin-type proteolytic enzymes. Particularly preferredis bacterial serine proteolytic enzyme obtained from Bacillus subtilisand/or Bacillus licheniformis.

Suitable proteolytic enzymes include Novo Industri A/S Alcalase(preferred), Esperase®, Savinase® (Copenhagen, Denmark), Gist-brocades'Maxatase®, Maxacal® and Maxapem 15® (protein engineered Maxacal®)(Delft, Netherlands), and subtilisin BPN and BPN'(preferred), which arecommercially available. Preferred proteolytic enzymes are also modifiedbacterial serine proteases, such as those made by GenencorInternational, Inc. (San Francisco, Calif.) which are described inEuropean Patent 251,446B, granted Dec. 28, 1994 (particularly pages 17,24 and 98) and which are also called herein “Protease B”. U.S. Pat. No.5,030,378, Venegas, issued Jul. 9, 1991, refers to a modified bacterialserine proteolytic enzyme (Genencor International) which is called“Protease A” herein (same as BPN'). In particular see columns 2 and 3 ofU.S. Pat. No. 5,030,378 for a complete description, including aminosequence, of Protease A and its variants. Other proteases are sold underthe tradenames: Primase, Durazym, Opticlean and Optimase. Preferredproteolytic enzymes, then, are selected from the group consisting ofAlcalase® (Novo Industri A/S), BPN', Protease A and Protease B(Genencor), and mixtures thereof. Protease B is most preferred.

Of particular interest for use herein are the proteases described inU.S. Pat. No. 5,470,733.

Also proteases described in co-pending application U.S. Ser. No.08/136,797 can be included in the detergent composition of theinvention.

Another preferred protease, referred to as “Protease D” is a carbonylhydrolase variant having an amino acid sequence not found in nature,which is derived from a precursor carbonyl hydrolase by substituting adifferent amino acid for a plurality of amino acid residues at aposition in said carbonyl hydrolase equivalent to position +76,preferably also in combination with one or more amino acid residuepositions equivalent to those selected from the group consisting of +99,+101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156,+166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265,and/or +274 according to the numbering of Bacillus amyloliquefacienssubtilisin, as described in WO 95/10615 published Apr. 20, 1995 byGenencor International (A. Baeck et al. entitled “Protease-ContainingCleaning Compositions” having U.S. Ser. No. 08/322,676, filed Oct. 13,1994).

Useful proteases are also described in PCT publications: WO 95/30010published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/30011published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/29979published Nov. 9, 1995 by The Procter & Gamble Company.

Protease enzyme may be incorporated into the compositions in accordancewith the invention at a level of from 0.0001% to 2% active enzyme byweight of the composition.

Amylase—Amylases (a and/or B) can be included for removal ofcarbohydrate-based stains. Suitable amylases are Termamyl® (NovoNordisk), Fungamyl® and BAN® (Novo Nordisk). The enzymes may be of anysuitable origin, such as vegetable, animal, bacterial, fungal and yeastorigin. Amylase enzymes are normally incorporated in the detergentcomposition at levels from 0.0001% to 2%, preferably from about 0.0001%to about 0.5%, more preferably from about 0.001% to about 0.1%, evenmore preferably from about 0.001% to about 0.001% of active enzyme byweight of the detergent composition.

Amylase enzymes also include those described in WO95/26397 and inco-pending application by Novo Nordisk PCT/DK96/00056. Other specificamylase enzymes for use in the detergent compositions of the presentinvention therefore include:

(a) α-amylases characterised by having a specific activity at least 25%higher than the specific activity of Termamyl® at a temperature range of25° C. to 55° C. and at a pH value in the range of 8 to 10, measured bythe Phadebas® α-amylase activity assay. Such Phadebas® α-amylaseactivity assay is described at pages 9-10, WO95/26397.(b) α-amylases according (a) comprising the amino sequence shown in theSEQ ID listings in the above cited reference. or an α-amylase being atleast 80% homologous with the amino acid sequence shown in the SEQ IDlisting.(c) α-amylases according (a) obtained from an alkalophilic Bacillusspecies, comprising the following amino sequence in the N-terminal:His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp.

A polypeptide is considered to be X % homologous to the parent amylaseif a comparison of the respective amino acid sequences, performed viaalgorithms, such as the one described by Lipman and Pearson in Science227, 1985, p. 1435, reveals an identity of X %

(d) α-amylases according (a-c) wherein the α-amylase is obtainable froman alkalophilic Bacillus species; and in particular, from any of thestrains NCIB 12289, NCIB 12512, NCIB 12513 and DSM 935.

In the context of the present invention, the term “obtainable from” isintended not only to indicate an amylase produced by a Bacillus strainbut also an amylase encoded by a DNA sequence isolated from such aBacillus strain and produced in an host organism transformed with saidDNA sequence.

(e) α-amylase showing positive immunological cross-reactivity withantibodies raised against an α-amylase having an amino acid sequencecorresponding respectively to those α-amylases in (a-d).(f) Variants of the following parent α-amylases which (i) have one ofthe amino acid sequences shown in corresponding respectively to thoseα-amylases in (a-e), or (ii) displays at least 80% homology with one ormore of said amino acid sequences, and/or displays immunologicalcross-reactivity with an antibody raised against an α-amylase having oneof said amino acid sequences, and/or is encoded by a DNA sequence whichhybridizes with the same probe as a DNA sequence encoding an α-amylasehaving one of said amino acid sequence; in which variants:

-   -   1. at least one amino acid residue of said parent α-amylase has        been deleted; and/or    -   2. at least one amino acid residue of said parent α-amylase has        been replaced by a different amino acid residue; and/or    -   3. at least one amino acid residue has been inserted relative to        said parent α-amylase; said variant having an α-amylase activity        and exhibiting at least one of the following properties relative        to said parent α-amylase: increased thermostability, increased        stability towards oxidation, reduced Ca ion dependency,        increased stability and/or α-amylolytic activity at neutral to        relatively high pH values, increased α-amylolytic activity at        relatively high temperature and increase or decrease of the        isoelectric point (pI) so as to better match the pI value for        α-amylase variant to the pH of the medium. Said variants are        described in the patent application PCT/DK96/00056.

Other amylases suitable herein include, for example, α-amylasesdescribed in GB 1,296,839 to Novo; RAPIDASE®, InternationalBio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo isespecially useful. Engineering of enzymes for improved stability, e.g.,oxidative stability, is known. See, for example J. Biological Chem.,Vol. 260, No. 11, June 1985, pp. 6518-6521. Certain preferredembodiments of the present compositions can make use of amylases havingimproved stability in detergents such as automatic dishwashing types,especially improved oxidative stability as measured against areference-point of TERMAMYL® in commercial use in 1993. These preferredamylases herein share the characteristic of being “stability-enhanced”amylases, characterized, at a minimum, by a measurable improvement inone or more of: oxidative stability, e.g., to hydrogenperoxide/tetraacetylethylenediamine in buffered solution at pH 9-10;thermal stability, e.g., at common wash temperatures such as about 60°C.; or alkaline stability, e.g., at a pH from about 8 to about 11,measured versus the above-identified reference-point amylase. Stabilitycan be measured using any of the art-disclosed technical tests. See, forexample, references disclosed in WO 9402597. Stability-enhanced amylasescan be obtained from Novo or from Genencor International. One class ofhighly preferred amylases herein have the commonality of being derivedusing site-directed mutagenesis from one or more of the Bacillusamylases, especially the Bacillus α-amylases, regardless of whether one,two or multiple amylase strains are the immediate precursors. Oxidativestability-enhanced amylases vs. the above-identified reference amylaseare preferred for use, especially in bleaching, more preferably oxygenbleaching, as distinct from chlorine bleaching, detergent compositionsherein. Such preferred amylases include (a) an amylase according to thehereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as furtherillustrated by a mutant in which substitution is made, using alanine orthreonine, preferably threonine, of the methionine residue located inposition 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®,or the homologous position variation of a similar parent amylase, suchas B. amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b)stability-enhanced amylases as described by Genencor International in apaper entitled “Oxidatively Resistant alpha-Amylases” presented at the207th American Chemical Society National Meeting, Mar. 13-17 1994, by C.Mitchinson. Therein it was noted that bleaches in automatic dishwashingdetergents inactivate alpha-amylases but that improved oxidativestability amylases have been made by Genencor from B. lichenifonnisNCIB8061. Methionine (Met) was identified as the most likely residue tobe modified. Met was substituted, one at a time, in positions 8, 15,197, 256, 304, 366 and 438 leading to specific mutants, particularlyimportant being M197L and M197T with the M197T variant being the moststable expressed variant. Stability was measured in CASCADE® andSUNLIGHT®; (c) particularly preferred amylases herein include amylasevariants having additional modification in the immediate parent asdescribed in WO 9510603 A and are available from the assignee, Novo, asDURAMYL®. Other particularly preferred oxidative stability enhancedamylase include those described in WO 9418314 to Genencor Internationaland WO 9402597 to Novo. Any other oxidative stability-enhanced amylasecan be used, for example as derived by site-directed mutagenesis fromknown chimeric, hybrid or simple mutant parent forms of availableamylases. Other preferred enzyme modifications are accessible. See WO9509909 A to Novo.

Various carbohydrase enzymes which impart antimicrobial activity mayalso be included in the present invention. Such enzymes includeendoglycosidase, Type II endoglycosidase and glucosidase as disclosed inU.S. Pat. Nos. 5,041,236, 5,395,541, 5,238,843 and 5,356,803 thedisclosures of which are herein incorporated by reference. Of course,other enzymes having antimicrobial activity may be employed as wellincluding peroxidases, oxidases and various other enzymes.

It is also possible to include an enzyme stabilization system into thecompositions of the present invention when any enzyme is present in thecomposition.

Perfumes—Perfumes and perfumery ingredients useful in the presentcompositions and processes comprise a wide variety of natural andsynthetic chemical ingredients, including, but not limited to,aldehydes, ketones, esters, and the like. Also included are variousnatural extracts and essences which can comprise complex mixtures ofingredients, such as orange oil, lemon oil, rose extract, lavender,musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, andthe like. Finished perfumes can comprise extremely complex mixtures ofsuch ingredients. Finished perfumes typically comprise from about 0.01%to about 2%, by weight, of the detergent compositions herein, andindividual perfumery ingredients can comprise from about 0.0001% toabout 90% of a finished perfume composition.

Non-limiting examples of perfume ingredients useful herein include:7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;ionone methyl; ionone gamma methyl; methyl cedrylone; methyldihydrojasmonate; methyl 1,6,10-trimethyl-2,5,9-cyclododecatrien-1-ylketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butanone;benzophenone; methyl beta-naphthyl ketone;6-acetyl-1,1,2,3,3,5-hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal,4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde;7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; iso-hexenyl cyclohexylcarboxaldehyde; formyl tricyclodecane; condensation products ofhydroxycitronellal and methyl anthranilate, condensation products ofhydroxycitronellal and indol, condensation products of phenylacetaldehyde and indol;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin;heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; coumarin;decalactone gamma; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acidlactone;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane;beta-naphthol methyl ether; ambroxane;dodecahydro-3a,6,6,9a-tetramethylnaphtho [2,1b]furan; cedrol,5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenylacetate; benzyl salicylate; cedryl acetate; andpara-(tert-butyl)cyclohexyl acetate.

Particularly preferred perfume materials are those that provide thelargest odor improvements in finished product compositions containingcellulases. These perfumes include but are not limited to: hexylcinnamic aldehyde; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate;beta-napthol methyl ether; methyl beta-naphthyl ketone;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyrane;dodecahydro-3a,6,6,9a-tetramethylnaphtho [2,1b]furan; anisaldehyde;coumarin; cedrol; vanillin; cyclopentadecanolide; tricyclodecenylacetate; and tricyclodecenyl propionate.

Other perfume materials include essential oils, resinoids, and resinsfrom a variety of sources including, but not limited to: Peru balsam,Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoinresin, coriander and lavandin. Still other perfume chemicals includephenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol,nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate, benzyl acetate, andeugenol. Carriers such as diethylphthalate can be used in the finishedperfume compositions.

Chelating Agents—The detergent compositions herein may also optionallycontain one or more iron and/or manganese chelating agents. Suchchelating agents can be selected from the group consisting of aminocarboxylates, amino phosphonates, polyfunctionally-substituted aromaticchelating agents and mixtures therein, all as hereinafter defined.Without intending to be bound by theory, it is believed that the benefitof these materials is due in part to their exceptional ability to removeiron and manganese ions from washing solutions by formation of solublechelates.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilo-tri-acetates, ethylenediamine tetrapro-prionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldi-glycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at lease low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred,these amino phosphonates to not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate (“EDDS”), especially the [S,S] isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

The compositions herein may also contain water-soluble methyl glycinediacetic acid (MGDA) salts (or acid form) as a chelant or co-builder.Similarly, the so called “weak” builders such as citrate can also beused as chelating agents.

If utilized, these chelating agents will generally comprise from about0.1% to about 15% by weight of the detergent compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by weight of such compositions.

Composition pH

Dishwashing compositions of the invention will be subjected to acidicstresses created by food soils when put to use, i.e., diluted andapplied to soiled dishes. If a composition with a pH greater than 7 isto be more effective, it preferably should contain a buffering agentcapable of providing a generally more alkaline pH in the composition andin dilute solutions, i.e., about 0.1% to 0.4% by weight aqueoussolution, of the composition. The pKa value of this buffering agentshould be about 0.5 to 1.0 pH units below the desired pH value of thecomposition (determined as described above). Preferably, the pKa of thebuffering agent should be from about 7 to about 10. Under theseconditions the buffering agent most effectively controls the pH whileusing the least amount thereof.

The buffering agent may be an active detergent in its own right, or itmay be a low molecular weight, organic or inorganic material that isused in this composition solely for maintaining an alkaline pH.Preferred buffering agents for compositions of this invention arenitrogen-containing materials. Some examples are amino acids such aslysine or lower alcohol amines like mono-, di-, and tri-ethanolamine.Other preferred nitrogen-containing buffering agents areTri(hydroxymethyl)amino methane (HOCH₂)₃CNH₃ (TRIS),2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-propanol,2-amino-2-methyl-1,3-propanol, disodium glutamate, N-methyldiethanolamide, 1,3-diamino-propanolN,N′-tetra-methyl-1,3-diamino-2-propanol, N,N-bis(2-hydroxyethyl)glycine(bicine) and N-tris (hydroxymethyl)methyl glycine (tricine). Mixtures ofany of the above are also acceptable. Useful inorganicbuffers/alkalinity sources include the alkali metal carbonates andalkali metal phosphates, e.g., sodium carbonate, sodium polyphosphate.For additional buffers see McCutcheon's EMULSIFIERS AND DETERGENTS,North American Edition, 1997, McCutcheon Division, MC Publishing CompanyKirk and WO 95/07971 both of which are incorporated herein by reference.

The buffering agent, if used, is present in the compositions of theinvention herein at a level of from about 0.1% to 15%, preferably fromabout 1% to 10%, most preferably from about 2% to 8%, by weight of thecomposition.

Calcium and/or Magnesium Ions

The presence of calcium and/or magnesium (divalent) ions improves thecleaning of greasy soils for various compositions, i.e., compositionscontaining alkyl ethoxy sulfates and/or polyhydroxy fatty acid amides.This is especially true when the compositions are used in softened waterthat contains few divalent ions. It is believed that calcium and/ormagnesium ions increase the packing of the surfactants at the oil/waterinterface, thereby reducing interfacial tension and improving greasecleaning.

Compositions of the invention herein containing magnesium and/or calciumions exhibit good grease removal, manifest mildness to the skin, andprovide good storage stability. These ions can be present in thecompositions herein at an active level of from about 0.1% to 4%,preferably from about 0.3% to 3.5%, more preferably from about 0.5% to1%, by weight.

Preferably, the magnesium or calcium ions are added as a hydroxide,chloride, acetate, formate, oxide or nitrate salt to the compositions ofthe present invention. Calcium ions may also be added as salts of thehydrotrope.

The amount of calcium or magnesium ions present in compositions of theinvention will be dependent upon the amount of total surfactant presenttherein. When calcium ions are present in the compositions of thisinvention, the molar ratio of calcium ions to total anionic surfactantshould be from about 0.25:1 to about 2:1.

Formulating such divalent ion-containing compositions in alkaline pHmatrices may be difficult due to the incompatibility of the divalentions, particularly magnesium, with hydroxide ions. When both divalentions and alkaline pH are combined with the surfactant mixture of thisinvention, grease cleaning is achieved that is superior to that obtainedby either alkaline pH or divalent ions alone. Yet, during storage, thestability of these compositions becomes poor due to the formation ofhydroxide precipitates. Therefore, chelating agents discussedhereinbefore may also be necessary.

Other Ingredients—The detergent compositions will further preferablycomprise one or more detersive adjuncts selected from the following:soil release polymers, polymeric dispersants, polysaccharides,abrasives, bactericides, tarnish inhibitors, builders, enzymes,opacifiers, dyes, buffers, antifungal or mildew control agents, insectrepellents, perfumes, hydrotropes, thickeners, processing aids, sudsboosters, brighteners, anti-corrosive aids, stabilizers antioxidants andchelants. A wide variety of other ingredients useful in detergentcompositions can be included in the compositions herein, including otheractive ingredients, carriers, hydrotropes, antioxidants, processingaids, dyes or pigments, solvents for liquid formulations, solid fillersfor bar compositions, etc. If high sudsing is desired, suds boosterssuch as the C₁₀-C₁₆ alkanolamides can be incorporated into thecompositions, typically at 1%-10% levels. The C₁₀-C₁₄ monoethanol anddiethanol amides illustrate a typical class of such suds boosters. Useof such suds boosters with high sudsing adjunct surfactants such as theamine oxides, betaines and sultaines noted above is also advantageous.

An antioxidant can be optionally added to the detergent compositions ofthe present invention. They can be any conventional antioxidant used indetergent compositions, such as 2,6-di-tert-butyl-4-methylphenol (BHT),carbamate, ascorbate, thio sulfate, monoethanolamine(MEA),diethanolamine, triethanolamine, etc. It is preferred that theantioxidant, when present, be present in the composition from about0.001% to about 5% by weight.

Various detersive ingredients employed in the present compositionsoptionally can be further stabilized by absorbing said ingredients ontoa porous hydrophobic substrate, then coating said substrate with ahydrophobic coating. Preferably, the detersive ingredient is admixedwith a surfactant before being absorbed into the porous substrate. Inuse, the detersive ingredient is released from the substrate into theaqueous washing liquor, where it performs its intended detersivefunction.

To illustrate this technique in more detail, a porous hydrophobic silica(trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzymesolution containing 3%-5% of C₁₃₋₁₅ ethoxylated alcohol (EO 7) nonionicsurfactant. Typically, the enzyme/surfactant solution is 2.5× the weightof silica. The resulting powder is dispersed with stirring in siliconeoil (various silicone oil viscosities in the range of 500-12,500 can beused). The resulting silicone oil dispersion is emulsified or otherwiseadded to the final detergent matrix. By this means, ingredients such asthe aforementioned enzymes, bleaches, bleach activators, bleachcatalysts, photoactivators, dyes, fluorescers, fabric conditioners andhydrolyzable surfactants can be “protected” for use in detergents,including liquid laundry detergent compositions.

Further, these hand dishwashing detergent embodiments preferably furthercomprises a hydrotrope. Suitable hydrotropes include sodium, potassium,ammonium or water-soluble substituted ammonium salts of toluene sulfonicacid, naphthalene sulfonic acid, cumene sulfonic acid, xylene sulfonicacid.

The detergent compositions of this invention can be in any form,including granular, paste, gel or liquid. Highly preferred embodimentsare in liquid or gel form. Liquid detergent compositions can containwater and other solvents as carriers. Low molecular weight primary orsecondary alcohols exemplified by methanol, ethanol, propanol, andisopropanol are suitable. Monohydric alcohols are preferred forsolubilizing surfactant, but polyols such as those containing from 2 toabout 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g.,1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) canalso be used. The compositions may contain from 5% to 90%, typically 10%to 50% of such carriers.

An example of the procedure for making granules of the detergentcompositions herein is as follows:—Linear alkylbenzenesulfonate, citricacid, sodium silicate, sodium sulfate perfume, diamine and water areadded to, heated and mixed via a crutcher. The resulting slurry is spraydried into a granular form.

An example of the procedure for making liquid detergent compositionsherein is as follows:—To the free water and citrate are added anddissolved. To this solution amine oxide, betaine, ethanol, hydrotropeand nonionic surfactant are added. If free water isn't available, thecitrate are added to the above mix then stirred until dissolved. At thispoint, an acid is added to neutralize the formulation. It is preferredthat the acid be chosen from organic acids such as maleic and citric,however, inorganic mineral acids may be employed as well. In preferredembodiments these acids are added to the formulation followed by diamineaddition. AExS is added last.

Non-Aqueous Liquid Detergents

The manufacture of liquid detergent compositions which comprise anon-aqueous carrier medium can be prepared according to the disclosuresof U.S. Pat. Nos. 4,753,570; 4,767,558; 4,772,413; 4,889,652; 4,892,673;GB-A-2,158,838; GB-A-2,195,125; GB-A-2,195,649; U.S. Pat. No. 4,988,462;U.S. Pat. No. 5,266,233; EP-A-225,654 (Jun. 16, 1987); EP-A-510,762(Oct. 28, 1992); EP-A-540,089 (5/5/93); EP-A-540,090 (5/5/93); U.S. Pat.No. 4,615,820; EP-A-565,017 (Oct. 13, 1993); EP-A-030,096 (Jun. 10,1981), incorporated herein by reference. Such compositions can containvarious particulate detersive ingredients stably suspended therein. Suchnon-aqueous compositions thus comprise a LIQUID PHASE and, optionallybut preferably, a SOLID PHASE, all as described in more detailhereinafter and in the cited references.

The compositions of this invention can be used to form aqueous washingsolutions for use hand dishwashing. Generally, an effective amount ofsuch compositions is added to water to form such aqueous cleaning orsoaking solutions. The aqueous solution so formed is then contacted withthe dishware, tableware, and cooking utensils.

An effective amount of the detergent compositions herein added to waterto form aqueous cleaning solutions can comprise amounts sufficient toform from about 500 to 20,000 ppm of composition in aqueous solution.More preferably, from about 800 to 5,000 ppm of the detergentcompositions herein will be provided in aqueous cleaning liquor.

Method of Use for Hand Dishwashing

The present invention also relates to a method for providing increasedsuds volume and increased suds retention while hand washing dishware orcookware articles in need of cleaning, comprising the step of contactingsaid articles with an aqueous solution of a detergent compositionsuitable for use in hand dishwashing, said composition comprising:

-   -   a) an effective amount of a polymeric suds stabilizer as        hereinbefore defined;    -   b) an effective amount of a detersive surfactant; and    -   c) the balance carriers and other adjunct ingredients;    -   provided the pH of a 10% aqueous solution of said composition is        from about 4 to about 12.

The present invention also relates to a means for preventing theredeposition of grease, oils, and dirt, especially grease, from the handwashing solution onto dishware. This method comprises contacting anaqueous solution of the compositions of the present invention withsoiled dishware and washing said dishware with said aqueous solution.

An effective amount of the detergent compositions herein added to waterto form aqueous cleaning solutions according to the method of thepresent invention comprises amounts sufficient to form from about 500 to20,000 ppm of composition in aqueous solution. More preferably, fromabout 800 to 2,500 ppm of the detergent compositions herein will beprovided in aqueous cleaning liquor.

The liquid detergent compositions of the present invention are effectivefor preventing the redeposition of grease from the wash solution backonto the dishware during washing. One measure of effectiveness of thecompositions of the present invention involves redeposition tests. Thefollowing test and others of similar nature are used to evaluate thesuitability of the formulas described herein.

A polyethylene 2 L graduated cylinder is filled to the 1 L graduationmark with an aqueous (water=7 grain) solution comprising from about 500to about 20,000 ppm of a liquid detergent composition according to thepresent invention. A synthetic greasy soil composition is then added tothe cylinder and the solution is agitated. After a period of time thesolution is decanted from the graduated cylinder and the interior wallsof the graduated cylinder are rinsed with a suitable solvent orcombination of solvents to recover any re-deposited greasy soil. Thesolvent is removed and the weight of greasy soil which remains insolution is determined by subtracting the amount of soil recovered fromthe amount initially added to the aqueous solution.

Other re-deposition test include immersion of tableware, flatware, andthe like and recovering any re-deposited soil.

The above test can be further modified to determine the increased amountof suds volume and suds duration. The solution is first agitated thensubsequently challenged with portions of greasy soil with agitationbetween each subsequent soil addition. The suds volume can be easilydetermined by using the vacant volume of the 2 L cylinder as a guide.

Compositions for Personal Care Products

Shampoos and Hand and/or Body Wash

In addition to the polymers of the present invention, beauty care andpersonal care products, such as shampoos and soaps for hand and/or bodywash, of the present invention contain adjunct ingredients. Additionalbackground on such products is provided by PCT application serial numberPCT/US98/04474, filed Mar. 6, 1998 and published as WO 98/38973,incorporated herein by reference in its entirety.

Pearlescent additives, also known as pearlizing agents, are added tobeauty and personal care products such as hair and skin care products toprovide a pearly appearance to the products. Chemicals which are tiny(micron size) needles or platelets often exhibit this pearly appearance.Materials which exhibit this effect are ethylene glycol mono- anddi-stearate, TiO₂ coated mica, bismuth oxychloride, and natural motherof pearl. Many organic materials exhibit this pearlescence provided theycan be produced in an appropriate needle or platelet shape. Ethyleneglycol distearate (EGDS) or ethylene glycol monostearate (EGMS) are themost commonly utilized pearlizing agents.

A stable, mild free flowing cold pearlizing concentrate is typicallyprepared using i) a pearlizing agent of this invention, preferably aglycol stearate; ii) a nonionic surfactant; iii) an amphotericsurfactant emulsifier and stabilizer, iv) a glycol emulsifier and v)water; to obviate the use of cocodiethanolamide and provide excellentcompatibility with any ionic surfactant. The concentrate will typicallybe essentially free of anionic surfactants such that the concentrate iscompatible with essentially any ionic surfactants that may be used inthe personal care product to which this concentrate is added.

The pearlizing agent comprises from about 5% to about 40%, preferablyfrom about 10% to about 30% and most preferably from about 15% to about25%, by weight based on the total weight of the concentrate.

The pearlizing agent can be selected from the group consisting ofhydroxyl stearate, polyethylene glycol mono- and di-stearates, ethyleneglycol mono- and distearates, stearic monoethanolamide, and mixturesthereof. The preferred agents are polyethylene glycol mono- anddistearates, and ethylene glycol mono- and di-stearates. The mostpreferred pearlizing agents for use are: ethylene glycol mono- anddi-stearates.

The fatty acid based member must be derived from a fatty acid feedstock(which includes free fatty acids, carboxylate salts, fatty mono-, di-and/or tri-glycerides) which consists of at least about 90% by weight ofoctadecanoic acid, i.e. the saturated fatty acid having one carboxylgroup (or derivative thereof) and a seventeen carbon alkyl tailcovalently bonded thereto. Stearic acid is available commercially indifferent grades, typically containing at least some portion of palmiticacid, i.e. the saturated fatty acid having one carboxyl group, and afifteen carbon alkyl tail covalently bonded thereto. For example,stearic acid is available in grades of 37.5% (nominal) and 42.5%(nominal) purity. Thus, those grades of stearic acid wherein less thanabout 90% of the fatty acid chains are octadecanoic acid will not beuseful in making the fatty acid based member used herein, unless thestearic acid is first purified to remove a sufficient number of specieswhich are not derived from octadecanoic acid. A useful grade of stearicacid is the 95% (nominal) grade the CTFA specifications of which are92.5% to 97.5% stearic acid and a maximum of 5% palmitic acid. A fattyacid comprised of 90% stearic acid and 10% palmitic acid should also beuseful.

The pearlizing agent is most useful as a concentrate with othercomponents, e.g. those other components as described in published PatentCooperation Treaty Application No. WO 98/38973, published on Sep. 11,1998, the disclosure of which is incorporated herein by reference in itsentirety.

A second component of the beauty and personal care product is a nonionicsurfactant. This surfactant can function as an emulsifier and stabilizerin the formulation. The term “nonionic surfactant” as utilized hereinencompasses mixtures of nonionic surfactants.

Examples of useful nonionic surfactants include condensates of ethyleneoxide with a hydrophobic moiety which has an average hydrophiliclipophilic balance (HLB) between about 8 to about 16, and morepreferably, between about 10 and about 12.5. These surfactants includethe condensation products of primary or secondary aliphatic alcoholshaving from about 8 to about 24 carbon atoms, in either straight orbranched chain configuration, with from about 2 to about 40, andpreferably between about 2 and about 9 moles of ethylene oxide per moleof alcohol.

In a preferred embodiment the aliphatic alcohol comprises between about9 and about 18 carbon atoms and is ethoxylated with between about 3 andabout 12 moles of ethylene oxide per mole of aliphatic alcohol.Especially preferred are the about 12 to about 15 carbon primary alcoholethoxylates containing about 5 to about 9 moles of ethylene oxide permole of alcohol. One such material is commercially sold under the tradename NEODOL 25-9 by Shell Chemical Company. Other commercial nonionicsurfactants include NEODOL 25-6.5 and NEODOL 25-7 sold by Shell ChemicalCompany.

Other suitable nonionic surfactants include the condensation products ofabout 6 to about 12 carbon atom alkyl phenols with about 3 to about 30,and preferably between about 5 and 14 moles of ethylene oxide. Examplesof such surfactants are sold under the trade manes Igepal CO 530, IgepalCO 630, Igepal C0720 and Igepal CO 730 by Rhodia, Inc. Still othersuitable nonionic surfactants are described in U.S. Pat. No. 3,976,586.To the extent necessary, this patent is expressly incorporated byreference. Most preferred for use are mixed linear alcohol ethoxylatessuch as Laureth-7 sold as Rhodasurf L-790 by Rhône-Poulenc Inc.

The nonionic surfactant is incorporated in the cold pearlizingconcentrate in an amount of from about 3% to about 30%; preferably fromabout 8% to about 25% and most preferably from about 10% to 20%, basedon the total weight of the concentrate.

An amphoteric surfactant comprises the third component of the presentinvention. The term “amphoteric surfactant” as utilized hereinencompasses one or more amphoteric surfactants such as mixtures ofamphoteric surfactants. Preferably, amphoteric surfactants known as thebetaines, their derivatives, and mixtures thereof are incorporated toprovide an enhanced pearlizing effect.

Examples of suitable amphoteric surfactants include the alkali metal,alkaline earth metal, ammonium or substituted ammonium salts of alkylamphocarboxy glycinates and alkyl amphocarboxypropionates, alkylamphodipropionates, alkyl amphodiacetates, alkyl amphoglycinates andalkyl amphopropionates wherein alkyl represents an alkyl group having 6to 20 carbon atoms. Other suitable amphoteric surfactants include alkyliminopropionates, alkyl iminodipropionates and alkylamphopropylsulfonates having between 12 and 18 carbon atoms; alkylbetaines and amidopropyl betaines and alkyl sultaines andalkylamidopropylhydroxy sultaines wherein alkyl represents an alkylgroup having 6 to 20 carbon atoms.

Particularly useful amphoteric surfactants include both mono anddicarboxylates such as those of the formulae:

wherein R is an alkyl group of 6-20 carbon atoms, x is 1 or 2 and M ishydrogen or sodium. Mixtures of the above structures are particularlypreferred.

Other formulae for the above amphoteric surfactants include thefollowing:

where R is a alkyl group of 6-20 carbon atoms and M is potassium, sodiumor a monovalent cation.

Of the above amphoteric surfactants, particularly preferred are thealkali salts of alkyl amphodipropionates, alkyl amphodiacetates, alkylamphoglycinates, alkyl amphopropyl sulfonates and alkyl amphopropionateswherein alkyl represents an alkyl group having 6 to 20 carbon atoms.Even more preferred are compounds wherein the alkyl group is derivedfrom coconut oil or is a lauryl group, for examplecocoamphodipropionate. Such cocoamphodipropionate surfactants arecommercially sold under the trademarks MIRANOL C2M-SF CONC. and MIRANOLFBS by Rhodia, Inc.

Other commercially useful amphoteric surfactants include:

-   -   cocoamphoacetate (sold under the trademarks MIRANOL ULTRA C-32        and MIRAPON FA),    -   cocoamphopropionate (sold under the trademarks MIRANOL CMSF        CONC. and MIRAPON FAS),    -   cocoamphodiacetate (sold under the trademarks MIRANOL C2M CONC.        and MIRAPON FB),    -   lauroamphoacetate (sold under the trademarks MIRANOL HM CONC.        and MIRAPON LA),    -   lauroamphodiacetate (sold under the trademarks MIRANOL H2M CONC.        and MIRAPON LB),    -   lauroamphodipropionate (sold under the trademarks MIRANOL H2M-SF        CONC. AND MIRAPON LBS),    -   lauroamphodiacetate obtained from a mixture of lauric and        myristic acids (sold under the trademark MIRANOL BM CONC.), and    -   cocoamphopropyl sulfonate (sold under the trademark MIRANOL CS        CONC.)    -   caproamphodiacetate (sold under the trademark MIRANOL S2M        CONC.),    -   caproamphoacetate (sold under the trademark MIRANOL SM CONC.),    -   caproamphodipropionate (sold under the trademark MIRANOL KM-SF        CONC.), and    -   stearoamphoacetate (sold under the trademark MIRANOL DM).

The most preferred amphoteric surfactant for use is cocoamphoacetate. Itcan be present from 0% to 10% based on the total weight of theconcentrate. Preferably, cocoamphoacetate will comprise from about 1% toabout 7% and most preferably from about 2% to about 4% of theconcentrate.

Also useful herein are the betaines and amidobetaines which arecompounds of the general structure:

respectively wherein R₂ is C₈-C₂₂ alkyl or alkenyl; R₃ is H or C₁-C₄alkyl; and R₄ is H or C₁-C₄ alkyl.

The betaines useful herein include the high alkyl betaines such ascocodimethyl carboxymethyl betaine, lauryl dimethyl carboxymethylbetaine, lauryl dimethyl alpha-carboxy-ethyl betaine, cetyl dimethylcarboxymethyl betaine, lauryl bis-(2-hydroxy-ethyl)carboxy methylbetaine, stearyl bis-(2-hydroxy-propyl)carboxymethyl betaine, oleyldimethyl gamma-carboxypropyl betaine, and laurylbis-(2-hydroxypropyl)alpha-carboxyethyl betaine. The sulfobetaines arealso preferred and may be represented by cocodimethyl sulfopropylbetaine, stearyldimethyl sulfopropyl betaine, lauryl dimethyl sulfoethylbetaine, lauryl bis-(2-hydroxy-ethyl)sulfopropyl betaine and mixturesthereof. A particularly preferred composition utilizes cocoamidopropylbetaine.

Most preferably, the amphoteric surfactant can be cocoamphoacetate andcocoamidopropyl betaine acting as amphoteric co-emulsifiers.

The amphoteric surfactant can be present from about 2% to about 20%weight percent based on the total weight of the pearlizing concentrate.Preferably, the amphoteric will comprise from about 4% to about 16%,most preferably from about 6% to about 10%, of the pearlizingconcentrate.

The fourth component consists of a glycol emulsifier. Propylene glycol(1,2, and 1, 3) and other alcohols such as 1,3-butylene glycol,2,3-butylene glycol, ethylene glycol and mixtures thereof are usefulemulsifiers. The glycol emulsifier can be present from 0% to about 15%,preferably from about 1% to about 10% and most preferably from about 2%to about 5%.

For the fifth component, the remainder is water, preferably deionized.Generally, water is added in an amount of from about 20% to about 70%,preferably from about 30% to about 60%, and most preferably from about40% to about 55% based on the total weight of the concentrate.

Non-essential optional components can be utilized in the concentrates ofthe present invention as a convenient means of incorporation into beautyand personal care products. Such conventional optional ingredients arewell known to those skilled in the art, e.g., preservatives such asbenzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea;thickeners and viscosity modifiers such as block polymers of ethyleneoxide and propylene oxide, e.g. ANTAROX F-88 (Rhodia, Inc.), sodiumchloride, sodium sulfate, polyvinyl alcohol, and ethyl alcohol; pHadjusting agents such as citric acid, succinic acid, phosphoric acid,sodium hydroxide, sodium carbonate; perfumes; dyes; and sequesteringagents such as disodium ethylenediamine tetra-acetate. Such agentsgenerally are used individually at levels of from 0% to about 2%,preferably from 0.01% to about 1.0% by weight of the concentrate.

The pH of the concentrate compositions is not critical and can be in therange of from about 2 to about 12, preferably from about 4 to about 10and most preferably from about 6 to about 8. The pH can be adjustedusing a buffer such as citric acid.

The order of addition to the mixing tank of the individual components ofthe concentrate is not critical nor is the reasonably elevatedtemperature; however, preferably the water and pearlizing agent areintimately blended at from about 50° to about 90° C., more preferablyfrom about 70° to about 80° C. with high agitation until the pearlizingagent is emulsified. The nonionic and amphoteric surfactants are thenblended into the mix until the mixture is clear. The mixture is thenallowed to cool to room temperature. Generally, the concentrate can bestored at a temperature of from about 0° C. to about 45° C., preferablyfrom about 15° C. to about 35° C. for at least one day and preferablytwo days in order to fully develop its pearlizing characteristics.

The personal care compositions may further comprise a silicone compound.As referred to herein, a silicone compound is a nonfunctionalizedsiloxane having a viscosity of from about 5 to about 600,000 cs(centistoke), and preferably from about 350 to about 10,000 cs, at 25°C. The so-called “rigid silicones”, as described in U.S. Pat. No.4,902,499, herein incorporated by reference, having a viscosity above600,000 cs at 20° C., e.g., 700,000 cs plus, and a weight averagemolecular weight of at least about 500,000, also are useful. Thesilicone compound is typically a polydimethylsiloxane, typically alinear polydimethylsiloxane terminated at each end with a trimethylsilylgroup. The silicone compound can be a dimethicone as specified by theCTFA, i.e. an alpha,omega-trimethylsilyl-polydimethylsiloxane having aviscosity at 25° C. of at least 25 centistokes and less than 60,000centistokes. The silicone compound is typically used in the context of ashampoo and is added to the composition in an amount sufficient toimpart improved combing and improved feel, such as softness, to the hairafter shampooing.

The silicone hair conditioning agent for use herein will preferably haveviscosity of from about 1,000 to about 2,000,000 centistokes at 25o C.,more preferably from about 10,000 to about 1,800,000, even morepreferably from about 100,000 to about 1,500,000. The viscosity can bemeasured by means of a glass capillary viscometer as set forth in DowCorning Corporate Test Method CTM0004, Jul. 20, 1970.

The silicone hair conditioning agent will be used in the shampoocompositions hereof at levels of from about 0.1% to about 10% by weightof the composition, preferably from about 0.5% to about 8%, morepreferably from about 1% to about 5%.

Suitable insoluble, nonvolatile silicone fluids include polyalkylsiloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyethersiloxane copolymer and mixtures thereof. However, other insoluble,nonvolatile silicone fluids having hair conditioning properties may beused. The term “nonvolatile” as used herein shall mean that the siliconematerial exhibits very low or no significant vapor pressure at ambientconditions, as is well understood in the art. The term “silicone fluid”shall mean flowable silicone materials having a viscosity of less than1,000,000 centistokes at 25° C. Generally, the viscosity of the fluidwill be between about 5 and 1,000,000 centistokes at 25° C., preferablybetween about 10 and about 100,000. The term “silicone”, as used herein,shall be synonomous with the term “polysiloxane”.

The nonvolatile polyalkylsiloxane fluids that may be used include, forexample, polydimethyl siloxanes. These siloxanes are available, forexample, from the General Electric Company as a VISCASIL series and fromDow Corning as the Dow Corning 200 series.

The polyalkylaryl siloxane fluids that may be used, also include, forexample, polymethylphenylsiloxanes. These siloxanes are available, forexample, from the General Electric Company as SF 1075 methyl phenylfluid or from Dow Corning as 556 Cosmetic Grade Fluid.

The polyether siloxane copolymers that may be used include, for example,a polypropylene oxide modified dimethylpolysiloxane (e.g., Dow CorningDC-1248) although ethylene oxide or mixtures of ethylene oxide andpropylene oxide may also be used. The ethylene oxide and polypropyleneoxide level must be sufficiently low to prevent solubility in water andthe composition hereof.

Silicone fluids hereof also include polyalkyl or polyaryl siloxanes withthe structure shown in U.S. Pat. No. 5,573,709, the disclosure of whichis incorporated herein by reference., herein R is alkyl or aryl, and xis an integer from about 7 to about 8,000 may be used. “A” representsgroups which block the ends of the silicone chains

The alkyl or aryl groups substituted on the siloxane chain (R) or at theends of the siloxane chains (A) may have any structure as long as theresulting silicones remain fluid at room temperature, are hydrophobic,are neither irritating, toxic nor otherwise harmful when applied to thehair, are compatible with the other components of the composition, arechemically stable under normal use and storage conditions, and arecapable of being deposited on and of conditioning hair.

Suitable A groups include methyl, methoxy, ethoxy, propoxy, and aryloxy.The two R groups on the silicone atom may represent the same group ordifferent groups. Preferably, the two R groups represent the same group.Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyland phenylmethyl. The preferred silicones are polydimethyl siloxane,polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxaneis especially preferred.

References disclosing suitable silicone fluids include U.S. Pat. No.2,826,551, Geen; U.S. Pat. No. 3,964,500, Drakoff, issued Jun. 22, 1976;U.S. Pat. No. 4,364,837, Pader; and British Patent 849,433, Woolston.All of these patents are incorporated herein by reference. Alsoincorporated herein by reference is Silicon Compounds distributed byPetrarch Systems, Inc., 1984. This reference provides an extensive(though not exclusive) listing of suitable silicone fluids.

Another silicone material that can be especially useful in the siliconeconditioning agents is insoluble silicone gum. The term “silicone gum”,as used herein, means polyorganosiloxane materials having a viscosity at25° C. of greater than or equal to 1,000,000 centistokes. Silicone gumsare described by Petrarch and others including U.S. Pat. No. 4,152,416,Spitzer et al., issued May 1, 1979 and Noll, Walter, Chemistry andTechnology of Silicones, New York: Academic Press 1968. Also describingsilicone gums are General Electric Silicone Rubber Product Data SheetsSE 30, SE 33, SE 54 and SE 76. All of these described references areincorporated herein by reference. The “silicone gums” will typicallyhave a mass molecular weight in excess of about 200,000, generallybetween about 200,000 and about 1,000,000. Specific examples includepolydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane)copolymer, poly(dimethylsiloxane) (diphenylsiloxane)(methylvinylsiloxane) copolymer and mixtures thereof.

Preferably the silicone hair conditioning agent comprises a mixture of apolydimethylsiloxane gum, having a viscosity greater than about1,000,000 centistokes and polydimethylsiloxane fluid having a viscosityof from about 10 centistokes to about 100,000 centistokes, wherein theratio of gum to fluid is from about 30:70 to about 70:30, preferablyfrom about 40:60 to about 60:40.

Another optional ingredient that can be included in the siliconeconditioning agent is silicone resin. Silicone resins are highlycrosslinked polymeric siloxane systems. The crosslinking is introducedthrough the incorporation of trifunctional and tetrafunctional silaneswith monofunctional or difunctional, or both, monomer units duringmanufacture of the silicone resin. As is well understood in the art, thedegree of crosslinking that is required in order to result in a siliconeresin will vary according to the specific silane units incorporated intothe silicone resin. In general, silicone materials which have asufficient level of trifunctional and tetrafunctional siloxane monomerunits (and hence, a sufficient level of crosslinking) such that they drydown to a rigid, or hard, film are considered to be silicone resins. Theratio of oxygen atoms to silicon atoms is indicative of the level ofcrosslinking in a particular silicone material. Silicone materials whichhave at least about 1.1 oxygen atoms per silicon atom will generally besilicone resins herein. Preferably, the ratio of oxygen:silicon atoms isat least about 1.2:1.0. Silanes used in the manufacture of siliconeresins include monomethyl-, dimethyl-, monophenyl, diphenyl-,methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, andtetra-chlorosilane, with the methyl-substituted silanes being mostcommonly utilized. Preferred resins are offered by General Electric asGE SS4230 and SS4267. Commercially available silicone resins willgenerally be supplied in an unhardened form in a low viscosity volatileor nonvolatile silicone fluid. The silicone resins for use herein shouldbe supplied and incorporated into the present compositions in suchunhardened form, as will be readily apparent to those skilled in theart.

Background material on silicones including sections discussing siliconefluids, gums, and resins, as well as manufacture of silicones, can befound in Encyclopedia of Polymer Science and Engineering, Volume 15,Second Edition, pp 204-308, John Wiley & Sons, Inc., 1989, incorporatedherein by reference.

Silicone materials and silicone resins in particular, can convenientlybe identified according to a shorthand nomenclature system well known tothose skilled in the art as “MDTQ” nomenclature. Under this system, thesilicone is described according to presence of various siloxane monomerunits which make up the silicone. Briefly, the symbol M denotes themonofunctional unit (CH₃)₃SiO_(0.5); D denotes the difunctional unit(CH₃)₂SiO; T denotes the trifunctional unit (CH₃)SiO_(1.5); and Qdenotes the quadri- or tetra-functional unit SiO₂. Primes of the unitsymbols, e.g., M′, D′, T′, and Q′ denote substituents other than methyl,and must be specifically defined for each occurrence. Typical alternatesubstituents include groups such as vinyl, phenyls, amines, hydroxyls,etc. The molar ratios of the various units, either in terms ofsubscripts to the symbols indicating the total number of each type ofunit in the silicone (or an average thereof) or as specificallyindicated ratios in combination with molecular weight complete thedescription of the silicone material under the MDTQ system. Higherrelative molar amounts of T, Q, T′ and/or Q′ to D, D′, M and/or or M′ ina silicone resin is indicative of higher levels of crosslinking. Asdiscussed before, however, the overall level of crosslinking can also beindicated by the oxygen to silicon ratio.

The silicone resins for use herein which are preferred are MQ, MT, MTQ,MQ and MDTQ resins. Thus, the preferred silicone substituent is methyl.Especially preferred are MQ resins wherein the M:Q ratio is from about0.5:1.0 to about 1.5:1.0 and the average molecular weight of the resinis from about 1000 to about 10,000.

The weight ratio of the nonvolatile silicone fluid component to thesilicone resin component is from about 4:1 to about 400:1, preferablythis ratio is from about 9:1 to about 200:1, more preferably from about19:1 to about 100:1, particularly when the silicone fluid component is apolydimethylsiloxane fluid or a mixture of polydimethylsiloxane fluidand polydimethylsiloxane gum as described above.

The shampoo will contain a detersive sufactant. These include anionic,cationic, nonionic surfactants, amphoteric surfactants, zwitterionicsurfactants. Examples of anionic surfactants are described in U.S. Pat.No. 5,573,709, the entire disclosure of which is incorporated byreference. However, the shampoo will typically be essentially free ofanionc surfactants, e.g. contain less than 0.5% by weight of speciesthat can properly be characterized as anionic surfactants. If theformulation does not include an anionic surfactant, cationic detersivesurfactants can also be used.

Nonionic detersive surfactants which can be used include those broadlydefined as compounds produced by the condensation of alkylene oxidegroups (hydrophilic in nature) with an organic hydrophobic compound,which may be aliphatic or alkyl aromatic in nature. Examples ofpreferred classes of nonionic detersive surfactants are

1. The polyethylene oxide condensates of alkyl phenols, e.g., thecondensation products of alkyl phenols having an alkyl group containingfrom about 6 to about 20 carbon atoms in either a straight chain orbranched chain configuration, with ethylene oxide, the said ethyleneoxide being present in amounts equal to from about 10 to about 60 molesof ethylene oxide per mole of alkyl phenol. The alkyl substituent insuch compounds may be derived from polymerized propylene, diisobutylene,octane, or nonane, for example.

2. Those derived from the condensation of ethylene oxide with theproduct resulting from the reaction of propylene oxide and ethylenediamine products which may be varied in composition depending upon thebalance between the hydrophobic and hydrophilic elements which isdesired. For example, compounds containing from about 40% to about 80%polyoxyethylene by weight and having a molecular weight of from about5,000 to about 11,000 resulting from the reaction of ethylene oxidegroups with a hydrophobic base constituted of the reaction product ofethylene diamine and excess propylene oxide, said base having amolecular weight of the order of about 2,500 to about 3,000, aresatisfactory.

3. The condensation product of aliphatic alcohols having from about 8 toabout 18 carbon atoms, in either straight chain or branched chainconfiguration, with ethylene oxide, e.g., a coconut alcohol ethyleneoxide condensate having from about 10 to about 30 moles of ethyleneoxide per mole of coconut alcohol, the coconut alcohol fraction havinfrom about 10 to about 14 carbon atoms.

4. Long chain tertiary amine oxides corresponding to the followinggeneral formula:

R¹R²R³N->0

wherein R¹ contains an alkyl, alkenyl or monohydroxy alkyl radical offrom about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxidemoieties, and from 0 to about 1 glyceryl moiety, and R² and R³ containfrom about 1 to about 3 carbon atoms and from 0 to about 1 hydroxygroup, e.g., methyl, ethyl, propyl, hydroxyethyl, or hydroxypropylradicals. The arrow in the formula is a conventional representation of asemipolar bond. Examples of amine oxides suitable for use in thisinvention include dimethyldodecylamine oxide, oleyldi(2-hydroxyethyl)amine oxide, dimethyloctylamine oxide, dimethyl-decylamine oxide,dimethyl-tetradecylamine oxide, 3,6,9-trioxaheptadecyldiethylamineoxide, di(2hydroxyethyl)-tetradecylamine oxide,2-dodecoxyethyldimethylamine oxide,3-dodecoxy-2-hydroxypropyldi(3-hydroxypropyl) amine oxide,dimethylhexadecylamine oxide.

5. Long chain tertiary phosphine oxides corresponding to the followinggeneral formula:

RR′R″P->0

wherein R contains an alkyl, alkenyl or monohydroxyalkyl radical rangingfrom about 8 to about 18 carbon atoms in chain length, from 0 to about10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety and R′and R″ are each alkyl or monohydroxyalkyl groups containing from about 1to about 3 carbon atoms. The arrow in the formula is a conventionalrepresentation of a semipolar bond. Examples of suitable phosphineoxides are: dodecyldimethylphosphine oxide, tetradecyldimethylphosphineoxide, tetradecylmethylethylphosphine oxide.3,6,9,-trioxaoctadecyldimethylphosphine oxide, cetyldimethylphosphineoxide, 3-dodecoxy-2-hydroxypropyldi (2-hydroxyethyl) phosphine oxide,stearyldimethylphosphine oxide, cetylethylpropylphosphine oxide,oleyldiethylphosphine oxide, dodecyldiethylphosphine oxide,tetradecyldiethylphosphine oxide, dodecyldipropylphosphine oxide,dodecyldi(hydroxymethyl)phosphine oxide,dodecyldi(2-hydroxyethyl)phosphine oxide,tetradecylmethyl-2-hydroxypropylphosphine oxide, oleydimethylphosphineoxide, 2-hydroxydodecyldimethylphosphine oxide.

6. Long chain dialkyl sulfoxides containing one short chain alkyl orhydroxy alkyl radical of from about 1 to about 3 carbon atoms (usuallymethyl) and one long hydrophobic chain which include alkyl, alkenyl,hydroxy alkyl, or keto alkyl radicals containing from about 8 to about20 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0to about 1 glyceryl moiety. Examples include: octadecyl methylsulfoxide, 2-ketotridecyl methyl sulfoxide, 3,6,9,-trixaoctadecyl2-hydroxyethyl sulfoxide, dodecyl methyl sulfoxide, oleyl3-hydroxypropyl sulfoxide, tetradecyl methyl sulfoxide,3-methoxytridecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide,3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

Zwitterionic detersive surfactants are exemplified by those which can bebroadly described as derivatives of aliphatic quaternary ammonium,phosphonium, and sulfonium compounds, in which the aliphatic radicalscan be straight or branched chain, and wherein one of the aliphaticsubstituents contains from about 8 to about 18 carbon atoms and onecontains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate,or phosphonate. A general formula for these compounds is: found in U.S.Pat. No. 5,573,709, which is incorporated herein by reference, whereinR² contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties andfrom 0 to about 1 glyceryl moiety; Y is selected from the groupconsisting of nitrogen, phosphorus, and sulfur atoms; R³ is an alkyl ormonohydroxyalkyl group containing about 1 to about 3 carbon atoms; X is1 when Y is a sulfur atom, and 2 when Y is a nitrogen or phosphorusatom; R⁴ is an alkylene or hydroxyalkylene of from about 1 to about 4carbon atoms and Z is a radical selected from the group consisting ofcarboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.

Examples of such surfactants include:

-   4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate;-   5-[S-3-hydroxypropyl-5-hexadecylsulfonio]-3-hydroxypentane-1-sulfate;-   3-[P,P-diethyl-P-3,6,9-trioxatetradexocylphosphonio]-2-hydroxy-propane-1-phosphate;-   3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio]-propane-1-phosphonate;-   3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate;-   3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate;-   4-[N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)ammonio]-butane-1-carboxylate;-   3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate;-   3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate; and-   5-[N,N-di    (3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-1-sulfate.

Other zwitterionics such as betaines can also useful in the presentinvention. Examples of betaines useful herein include the high alkylbetaines, such as coco dimethyl carboxymethyl betaine, cocoamidopropylbetaine, cocobetaine, lauryl amidopropyl betaine, oleyl betaine, lauryldimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethylbetaine, cetyl dimethyl carboxymethyl betaine, laurylbis-(2-hydroxyethyl) carboxymethyl betaine, stearylbis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethylgamma-carboxypropyl betaine, and laurylbis-(2-hydroxypropyl)alpha-carboxyethyl betaine. The sulfobetaines maybe represented by coco dimethyl sulfopropyl betaine, stearyl dimethylsulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, laurylbis-(2-hydroxyethyl) sulfopropyl betaine and the 1 like; amidobetainesand amidosulfobetaines, wherein the RCONH(CH₂)₃ radical is attached tothe nitrogen atom of the betaine are also useful in this invention.Preferred betaines for use in the present compositions arecocoamidopropyl betaine, cocobetaine, lauryl amidopropyl betaine, andoleyl betaine.

Examples of amphoteric detersive surfactants which can be used in thecompositions of the present invention are those which are broadlydescribed as derivatives of aliphatic secondary and tertiary amines inwhich the aliphatic radical can be straight or branched chain andwherein one of the aliphatic substituents contains from about 8 to about18 carbon atoms and one contains an anionic water solubilizing group,e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examplesof compounds falling within this definition are sodium3-dodecyl-aminopropionate, sodium 3-dodecylaminopropane sulfonate,sodium lauryl sarcosinate, N-alkyltaurines such as the one prepared byreacting dodecylamine with sodium isethionate according to the teachingof U.S. Pat. No. 2,658,072, N-higher alkyl aspartic acids such as thoseproduced according to the teaching of U.S. Pat. No. 2,438,091, and theproducts sold under the trade name “MIRANOL”™ and described in U.S. Pat.No. 2,528,378. Another detersive surfactant optional for use in thecompositions of the present invention is cocoamphocarboxy glycinate.

The most preferred shampoos of the present invention containcombinations of amphoteric surfactants, zwitterionic surfactants, andnonionic surfactants and are essentially free of anionic surfactants.The shampoos typically contain from about 0% to about 6% of amphotericsurfactants, about 0% to about 8% of zwitterionic surfactants, from 0%to about 14% of ethoxylated alkyl sulfates, and from about 0% to about10% of an optional anionic surfactant surfactants, e.g. about 3% toabout 7% alkyl sulfates, with a total surfactant level of from about 10%to about 25%.

The formulated shampoo and soap systems of the present invention cancontain a variety of non-essential optional components suitable forrendering such compositions more acceptable. Such conventional optionalingredients are well known to those skilled in the art, e.g.,preservatives such as benzyl alcohol, methyl paraben, propyl paraben andimidazolidinyl urea; cationic surfactants such as cetyl trimethylammonium chloride, lauryl trimethyl ammonium chloride, tricetyl methylammonium chloride, stearyldimethyl benzyl ammonium chloride, anddi(partially hydrogenated tallow)dimethylammonium chloride; thickenersand viscosity modifiers such as block polymers of ethylene oxide andpropylene oxide, e.g. ANTAROX F-88 (Rhodia, Inc.), sodium chloride,sodium sulfate, polyvinyl alcohol, and ethyl alcohol; pH adjustingagents such as citric acid, succinic acid, phosphoric acid, sodiumhydroxide, sodium carbonate; perfumes; dyes; and sequestering agentssuch as disodium ethylenediamine tetra-acetate. Such agents generallyare used individually at levels of from about 0.01% to about 10%,preferably from 0.5% to about 5.0% by weight of the composition.

Shampoos may also include antidandruff agents such as pyrithione salts,preferably zinc pyrithione, as disclosed by PCT application numberPCT/US98/04139, filed Mar. 4, 1998 and published as WO 98/41505,incorporated herein by reference in its entirety.

Hair Removal Personal Care Products

The foam enhancer of the present invention may also be employed withfoam forming shaving gels and shaving creams. Typical post foamingshaving gels are disclosed by U.S. Pat. Nos. 5,902,778 to Hartmann, etal; 5,858,343 to Szymczak; and 5,853,710 to Dehan, et al, all of whichare incorporated herein by reference in their entirety. Typical foamshaving creams are disclosed by U.S. Pat. Nos. 5,686,024 to Dahanayake,et al; 5,415,860 to Beucherie, et al; 5,902,574 to Stoner, et al; and5,104,643 to Grollier, et al, all of which are incorporated herein byreference in their entirety.

The foam enhancer is also useful in a foam dephilatory. An example of afoam dephilatory is disclosed in U.S. Pat. No. 4,734,099 to Cyprien.

Compositions and Methods of Use for Laundry Detergents

In addition to the polymers of the present invention (used as soilrelease agents), laundry detergents of the present invention (forwashing by hand or in a washing machine) further include adjunctingredients. A variety of such adjunct laundry detergent ingredients aredisclosed by PCT International Publication No. WO 98/39401, incorporatedherein by reference in its entirety.

In general, the laundry detergent compositions are solid granules,liquid or gel and comprise a major amount by weight of detergent and aminor amount of the soil release polymer of the present invention. Also,in general the method for washing fabric of the present inventioncomprises washing a fabric article in a washing medium comprised of amajor amount by weight of water and a first minor amount by weight ofdetergent and a second minor amount by weight of the soil releasepolymer. Minor amounts of adjunct components may also be present.

I. Aminoalkyl/alkoxysilane-silicone Compounds

One of the adjunct components of the compositions and methods of thisinvention is an aminosilicone compound, typically an aminosiliconecompound of the formula:

wherein:

R¹ and R⁸ are independently selected from the group consisting ofhydrogen, hydroxyl, alkyl (typically C₁-C₄) and alkoxy (typicallyC₁-C₄),

R², R³, R⁹, and R¹⁰ are independently selected from the group consistingof alkyl (typically C₁-C₄) and alkoxy (typically C₁-C₄), provided thatone of R², R³, R⁹, and R¹⁰ may be selected from the group consisting ofa primary amino-substituted alkyl group, and a secondaryamino-substituted alkyl group (typically an N-(amino-alkyl)-substitutedaminoalkyl group such that the compound will have both primary andsecondary amine functionality),

R⁴, R⁵, and R⁶ are independently selected from the group consisting ofalkyl (typically C₁-C₄) and aryl (typically phenyl),

R⁷ is selected from the group consisting of a primary amino-substitutedalkyl group, and a secondary amino-substituted alkyl group (typically anN-(aminoalkyl)-substituted aminoalkyl group such that the compound willhave both primary and secondary amine functionality),

m and n are numbers wherein m is greater than n (typically the ratio ofm:n is from about 2:1 to about 500:1, more typically from about 40:1 toabout 300:1 and most typically from about 85:1 to about 185:1) and thesum of n and m yield an aminosilicone compound with a viscosity of about10 to about 100,000 cps at 25° (typically the sum of n and m is fromabout 5 to about 600, more typically from about 50 to about 400 and mosttypically from about 135 to about 275).

The preparation and properties of silicone compounds is discussedgenerally in Silicones: Chemistry and Technology, pp. 21-31 and 75-90(CRC Press, Vulkan-Verlag, Essen, Germany, 1991) and in Harman et al.“Silicones”, Encyclopedia of Polymer Science and Engineering, vol. 15,pp. (John Wiley & Sons, Inc. 1989), the disclosures of which areincorporated herein by reference. Preferred aminosilicone compounds aredisclosed, for example in JP-047547 (J57161170) (Shinetsu Chem. Ind.KK). Particularly preferred aminosilicone compounds are the three offormula I wherein (1) R¹ and R⁸ are methoxy, R², R³, R⁴, R⁵, R⁶, R⁹, andR¹⁰ are methyl, R⁷ is N-aminoethyl-3-aminopropyl, m is about 135, and nis about 1.5, (2) R¹ and R⁸ are methoxy, R², R³, R⁴, R⁵, R⁶, R⁹, and R¹⁰are methyl, R⁷ is N-aminoethyl-3-aminopropyl, m is about 270, and n isabout 1.5, and (3) R¹ and R⁸ are ethoxy, R², R³, R⁴, R⁵, R⁶, R⁹, and R¹⁰are methyl, R⁷ is 3-aminopropyl, m is about 135, and n is about 1.5.Other aminosilicone compounds include those wherein R¹, R², and R⁸ areethoxy, R³ is 3-aminopropyl, R⁴, R⁵, R⁶, R⁹, and R¹⁰ are methyl, m isabout 8, and n is zero. Of course, for pure aminosilicone compounds, thenumbers m and n will be integers, but for mixtures of compounds, m and nwill be expressed as fractions or compound numbers which represent anaverage of the compounds present. Further, the formula above is notmeant to imply a block copolymer structure, thus, the aminosiliconecompound may have a random or block structure. Typically, at least about50% by weight of the R⁴, R⁵, and R⁶ groups will be methyl groups, moretypically at least about 90% and even more typically about 100%.

The aminosilicone compound typically will be in the form of a liquid orviscous oil at room temperature.

The aminosilicones described below in the context of the soluble powderdetergent compositions can be substituted for the aminosiliconesdescribed above.

II. Insoluble Carriers

While the aminosilicone can be used in certain compositions and methodsof this invention alone or as an aqueous emulsion, the aminosilicone ispreferably used in association with a water-insoluble solid carrier, forexample, clays, natural or synthetic silicates, silica, resins, waxes,starches, ground natural minerals, such as kaolins, clays, talc, chalk,quartz, attapulgite, montmorillonite, bentonite or diatomaceous earth,or ground synthetic minerals, such as silica, alumina, or silicatesespecially aluminum or magnesium silicates. Useful inorganic agentscomprise those of natural or synthetic mineral origin. Specific examplesof carriers include diatomaceous earths, e.g. Celite™ (Johns ManvilleCorp., Denver, Col.) and the smectite clays such as the saponites andthe montmorillonite colloidal clays such as Veegum™ and Van Gel™(Vanderbilt Minerals, Murray, Ky.), or Magnabrite™ (American ColloidCo., Skokie, Ill.). Synthetic silicate carriers include the hydrouscalcium silicate, Micro-Cel™ and the hydrous magnesium silicate Celkate™(Seegot, Inc., Parsippany, N.J.). Inosilicates carriers such as thenaturally-occurring calcium meta-silicates such as wollastonite,available as the NYAD™ wollastonite series (Processed Minerals Inc.,Willsboro, N.Y.) can also be mentioned. Synthetic sodium magnesiumsilicate clays, hectorite clays, and fumed silicas can also be mentionedas carriers. The carrier can be a very finely divided material ofaverage particle diameter below 0.1 micron. Examples of such carriersare fumed silica and precipitated silica; these generally have aspecific surface (BET) of above 40 m²/g.

The clays that are particularly useful elements of the compositions andmethods of this invention are those which cooperate with the siliconecompounds to wash laundry better than would be expected from the actionsof the individual components in detergent compositions. Such claysinclude the montmorillonite-containing clays which have swellingproperties (in water) and which are of smectite structure. Typical ofthe smectite clays for use in the present invention is bentonite andtypically the best of the bentonites are those which have a substantialswelling capability in water, such as the sodium bentonites, thepotassium bentonites, or which are swellable in the presence of sodiumor potassium ions, such as calcium bentonite. Such swelling bentonitesare also known as western or Wyoming bentonites, which are essentiallysodium bentonite. Other bentonites, such as calcium bentonite, arenormally non-swelling. Among the preferred bentonites are those ofsodium and potassium, which are normally swelling, and calcium andmagnesium, which are normally non-swelling, but are swellable. Of theseit is preferred to utilize calcium (with a source of sodium beingpresent) and sodium bentonites. The bentonites employed are not limitedto those produced in the United States of America, such as Wyomingbentonite, but also may be obtained from Europe, including Italy andSpain, as calcium bentonite, which may be converted to sodium bentoniteby treatment with sodium carbonate, or may be employed as calciumbentonite. Typically, the clay will have a high montmorillonite contentand a low content of cristobalite and/or quartz. Also, othermontmorillonite-containing smectite clays of properties like those ofthe bentonites described may be substituted in whole or in part for thebentonites described herein, but typically the clay will be a sodiumbentonite with high montmorillonite content and low cristobalite andquartz contents.

The swellable bentonites and similarly operative clays are of ultimateparticle sizes in the micron range, e.g., 0.01 to 20 microns and ofactual particle sizes less than 100 or 150 microns, such as 40 to 150microns or 45 to 105 microns. Such size ranges also apply to the zeolitebuilders, which will be described later herein. The bentonite and othersuch suitable swellable clays may be agglomerated to larger particlesizes too, such as up to 2 or 3 mm. in diameter.

The ratio of aminosilicone compound to carrier will typically range fromabout 0.001 to about 2, more typically from about 0.02 to about 0.5, andmost typically from about 0.1 to about 0.3.

III. Detergents

The methods and compositions of this laundry detergent invention allemploy a detergent, and optionally, other functional ingredients.Examples of the detergents and other functional ingredients that can beused are disclosed in U.S. Ser. No. 08/726,437, filed Oct. 4, 1996, thedisclosure of which is incorporated herein by reference. The detergentcan be selected from a wide variety of surface active agents.

A. Nonionic Surfactants

Nonionic surfactants, including those having an HLB of from 5 to 17, arewell known in the detergency art. Examples of such surfactants arelisted in U.S. Pat. No. 3,717,630, Booth, issued Feb. 20, 1973, and U.S.Pat. No. 3,332,880, Kessler et al., issued Jul. 25, 1967, each of whichis incorporated herein by reference. Nonlimiting examples of suitablenonionic surfactants which may be used in the present invention are asfollows:

-   (1) The polyethylene oxide condensates of alkyl phenols. These    compounds include the condensation products of alkyl phenols having    an alkyl group containing from about 6 to 12 carbon atoms in either    a straight chain or branched chain configuration with ethylene    oxide, said ethylene oxide being present in an amount equal to 5 to    25 moles of ethylene oxide per mole of alkyl phenol. The alkyl    substituent in such compounds can be derived, for example, from    polymerized propylene, diisobutylene, and the like. Examples of    compounds of this type include nonyl phenol condensed with about 9.5    moles of ethylene oxide per mole of nonyl phenol; dodecylphenol    condensed with about 12 moles of ethylene oxide per mole of phenol;    dinonyl phenol condensed with about 15 moles of ethylene oxide per    mole of phenol; and diisooctyl phenol condensed with about 15 moles    of ethylene oxide per mole of phenol. Commercially available    nonionic surfactants of this type include Igepal CO-630, marketed by    Rhodia, Inc. and Triton X-45, X-114, X-100, and X-102, all marketed    by Union Carbide.-   (2) The condensation products of aliphatic alcohols with from about    1 to about 25 moles of ethylene oxide. The alkyl chain of the    aliphatic alcohol can either be straight or branched, primary or    secondary, and generally contains from about 8 to about 22 carbon    atoms. Examples of such ethoxylated alcohols include the    condensation product of myristyl alcohol condensed with about 10    moles of ethylene oxide per mole of alcohol; and the condensation    product of about 9 moles of ethylene oxide with coconut alcohol (a    mixture of fatty alcohols with alkyl chains varying in length from    10 to 14 carbon atoms). Examples of commercially available nonionic    surfactants in this type include Tergitol 15-S-9, marketed by Union    Carbide Corporation, Neodol 45-9, Neodol 23-6.5, Neodol 45-7, and    Neodol 45-4, marketed by Shell Chemical Company.-   (3) The condensation products of ethylene oxide with a hydrophobic    base formed by the condensation of propylene oxide with propylene    glycol. The hydrophobic portion of these compounds typically has a    molecular weight of from about 1500 to 1800 and exhibits water    insolubility. The addition of polyoxyethylene moieties to this    hydrophobic portion tends to increase the water solubility of the    molecule as a whole, and the liquid character of the product is    retained up to the point where the polyoxyethylene content is about    50% of the total weight of the condensation product, which    corresponds to condensation with up to about 40 moles of ethylene    oxide. Examples of compounds of this type include certain of the    commercially available Pluronic surfactants, marketed by Wyandotte    Chemical Corporation.-   (4) The condensation products of ethylene oxide with the product    resulting from the reaction of propylene oxide and ethylenediamine.    The hydrophobic moiety of these products consists of the reaction    product of ethylenediamine and excess propylene oxide, said moiety    having a molecular weight of from about 2500 to about 3000. This    hydrophobic moiety is condensed with ethylene oxide to the extent    that the condensation product contains from about 40% to about 80%    by weight of polyoxyethylene and has a molecular weight of from    about 5,000 to about 11,000. Examples of this type of nonionic    surfactant include certain of the commercially available Tetronic    compounds, marketed by Wyandotte Chemical Corporation.-   (5) Semi-polar nonionic detergent surfactants include water-soluble    amine oxides containing one alkyl moiety of from about 10 to 18    carbon atoms and 2 moieties selected from the group consisting of    alkyl groups and hydroxyalkyl groups containing from 1 to about 3    carbon atoms; water-soluble phosphine oxides containing one alkyl    moiety of about 10 to 18 carbon atoms and 2 moieties selected from    the group consisting of alkyl groups and hydroxyalkyl groups    containing from about 1 to 3 carbons atoms; and water-soluble    sulfoxides containing one alkyl moiety of from about 10 to 18 carbon    atoms and a moiety selected from the group consisting of alkyl and    hydroxyalkyl moieties of from about 1 to 3 carbon atoms.

Preferred semi-polar nonionic detergent surfactants are the amine oxidedetergent surfactants having the formula

wherein R¹ is an alkyl, hydroxy alkyl, or alkyl phenyl group or mixturesthereof containing from about 8 to about 22 carbon atoms. R² is analkylene or hydroxy alkylene group containing from 2 to 3 carbon atomsor mixtures thereof, x is from 0 to about 3 and each R³ is an alkyl orhydroxy alkyl group containing from 1 to about 3 carbon atoms or apolyethylene oxide group containing from one to about 3 ethylene oxidegroups and said R³ groups can be attached to each other, e.g., throughan oxygen or nitrogen atom to form a ring structure.

Preferred amine oxide detergent surfactants are C₁₀-C₁₈ alkyl dimethylamine oxide, C₈-C₁₈ alkyl dihydroxy ethyl amine oxide, and C₈₋₁₂ alkoxyethyl dihydroxy ethyl amine oxide.

Nonionic detergent surfactants (1)-(4) are conventional ethoxylatednonionic detergent surfactants and mixtures thereof can be used.

Preferred alcohol ethoxylate nonionic surfactants for use in thecompositions of the liquid, powder, and gel applications arebiodegradable and have the formula

R(OC₂H₄)_(n)OH

wherein R is a primary or secondary alkyl chain of from about 8 to about22, preferably from about 10 to about 20 carbon atoms and n is anaverage of from about 2 to about 12, particularly from about 2 to about9. The nonionics have an HLB (hydrophilic-lipophilic balance) of fromabout 5 to about 17, preferably from about 6 to about 15. HLB is definedin detail in Nonionic Surfactants, by M. J. Schick, Marcel Dekker, Inc.,1966, pages 606-613, incorporated herein by reference. In preferrednonionic surfactants, n is from 3 to 7. Primary linear alcoholethoxylates (e.g., alcohol ethoxylates produced from organic alcoholswhich contain about 20% 2-methyl branched isomers, commerciallyavailable from Shell Chemical Company under the trademark Neodol) arepreferred from a performance standpoint.

Particularly preferred nonionic surfactants for use in liquid, powder,and gel applications include the condensation product of C₁₀ alcoholwith 3 moles of ethylene oxide; the condensation product of tallowalcohol with 9 moles of ethylene oxide; the condensation product ofcoconut alcohol with 5 moles of ethylene oxide; the condensation productof coconut alcohol with 6 moles of ethylene oxide; the condensationproduct of C₁₋₂ alcohol with 5 moles of ethylene oxide; the condensationproduct of C₁₂₋₁₃ alcohol with 6.5 moles of ethylene oxide, and the samecondensation product which is stripped so as to remove substantially alllower ethoxylate and nonethoxylated fractions; the condensation productof C₁₂₋₁₃ alcohol with 2.3 moles of ethylene oxide, and the samecondensation product which is stripped so as to remove substantially alllower ethoxylated and nonethoxylated fractions; the condensation productof C₁₂₋₁₃ alcohol with 9 moles of ethylene oxide; the condensationproduct of C₁₄₋₁₅ alcohol with 2.25 moles of ethylene oxide; thecondensation product of C₁₄₋₁₅ alcohol with 4 moles of ethylene oxide;the condensation product of C₁₄₋₁₅ alcohol with 7 moles of ethyleneoxide; and the condensation product of C₁₄₋₁₅ alcohol with 9 moles ofethylene oxide. For bar soap applications, nonionic surfactants arepreferably solids at room temperature with a melting point above about25° C., preferably above about 30° C. Bar compositions of the presentinvention made with lower melting nonionic surfactants are generally toosoft, not meeting the bar firmness requirements of the presentinvention.

Also, as the level of nonionic surfactant increases, i.e., above about20% by weight of the surfactant, the bar can generally become oily.

Examples of nonionic surfactants usable herein, but not limited to barapplications, include fatty acid glycerine and polyglycerine esters,sorbitan sucrose fatty acid esters, polyoxyethylene alkyl and alkylallyl ethers, polyoxyethylene lanolin alcohol, glycerine andpolyoxyethylene glycerine fatty acid esters, polyoxyethylene propyleneglycol and sorbitol fatty acid esters, polyoxyethylene lanolin, castoroil or hardened castor oil derivatives, polyoxyethylene fatty acidamides, polyoxyethylene alkyl amines, alkylpyrrolidone, glucamides,alkylpolyglucosides, and mono- and dialkanol amides.

Typical fatty acid glycerine and polyglycerine esters, as well astypical sorbitan sucrose fatty acid esters, fatty acid amides, andpolyethylene oxide/polypropylene oxide block copolymers are disclosed byU.S. Pat. No. 5,510,042, Hartman et al, incorporated herein byreference.

The castor oil derivatives are typically ethoxylated castor oil. It isnoted that other ethoxylated natural fats, oils or waxes are alsosuitable.

Polyoxyethylene fatty acid amides are made by ethoxylation of fatty acidamides with one or two moles of ethylene oxide or by condensing mono- ordiethanol amines with fatty acid.

Polyoxyethylene alkyl amines include those of formula:RNH—(CH₂CH₂O)_(n)—H, wherein R is C₆ to C₂₂ alkyl and n is from 1 toabout 100.

Monoalkanol amides include those of formula: RCONHR¹OH, wherein R isC₆-C₂₂ alkyl and R¹ is C₁ to C₆ alkylene. Dialkanol amides are typicallymixtures of:

diethanolamide: RCON(CH₂CH₂OH)₂;

amide ester: RCON(CH₂CH₂OH)—CH₂CH₂OOCR;

amine ester: RCOOCH₂CH₂NHCH₂CH₂OH; and

amine soap: RCOOH₂N(CH₂CH₂OH)₂,

wherein R in the above formulas is an alkyl of from 6 to 22 carbonatoms.

Examples of preferred but not limiting surfactants for detergent barproducts are the following:

Straight-Chain Primary Alcohol Alkoxylates

The deca-, undeca-, dodeca-, tetradeca-, and pentadeca-ethoxylates ofn-hexadecanol, and n-hexadecanol, and n-octadecanol having an HLB withinthe range recited herein are useful nonionics in the context of thisinvention. Exemplary ethoxylated primary alcohols useful herein as theconventional nonionic surfactants of the compositions are n-C₁₈EO(10);n-C₁₄EO(13); and n-C₁₀EO(11). The ethoxylates of mixed natural orsynthetic alcohols in the “tallow” chain length range are also usefulherein. Specific examples of such materials includetallow-alcohol-EO(11), tallow-alcohol-EO(18), and tallow-alcohol-EO(25).

Straight-Chain Secondary Alcohol Alkoxylates

The deca-, undeca-, dodeca-, tetradeca-, pentadeca-, octadeca-, andnonadeca-ethoxylates of 3-hexadecanol, 2-octadecanol, 4-eicosanol, and5-eicosanol having an HLB within the range recited herein are usefulconventional nonionics in the context of this invention. Exemplaryethoxylated secondary alcohols useful herein are 2-C₁₆EO(11);2-C₂₀EO(11); and 2-C₁₆EO(14).

Alkyl Phenol Alkoxylates

As in the case of the alcohol alkoxylates, the hexa-throughoctadeca-ethoxylates of alkylated phenols, particularly monohydricalkylphenols, having an HLB within the range recited herein are usefulas conventional nonionic surfactants in the instant compositions. Thehexa-through octadeca-ethoxylates of p-tridecylphenol,m-pentadecylphenol, and the like, are useful herein. Exemplaryethoxylated alkylphenols useful in the mixtures herein are:p-tridecylphenol EO(11) and p-pentadecylphenol EO(18). Especiallypreferred is Nonyl Nonoxynol-49 known as Igepal® DM-880 from Rhodia,Inc.

As used herein and as generally recognized in the art, a phenylene groupin the nonionic formula is the equivalent of an alkylene groupcontaining from 2 to 4 carbon atoms. For present purposes, nonionicscontaining a phenylene group are considered to contain an equivalentnumber of carbon atoms calculated as the sum of the carbon atoms in thealkyl group plus about 3.3 carbon atoms for each phenylene group.

Olefinic Alkoxylates

The alkenyl alcohols, both primary and secondary, and alkenyl phenolscorresponding to those disclosed immediately hereinabove can beethoxylated to an HLB within the range recited herein and used as theconventional nonionic surfactants of the instant compositions.

Branched Chain Alkoxylates

Branched chain primary and secondary alcohols which are available can beethoxylated and employed as conventional nonionic surfactants incompositions herein.

The above ethoxylated nonionic surfactants are useful in the presentcompositions alone or in combination, and the term “nonionic surfactant”encompasses mixed nonionic surface active agents.

Alkylpolysaccharides

Still further suitable nonionic surfactants of this invention includealkylpolysaccharides, preferably alkylpolyglycosides of the formula:

RO(C_(n)H_(2n)O)_(t)(Z)_(x)

wherein

Z is derived from glycose;

R is a hydrophobic group selected from the group consisting of aC₁₀-C₁₈, preferably a C₁₂-C₁₄, alkyl group, alkyl phenyl group,hydroxyalkyl group, hydroxyalkylphenyl group, and mixtures thereof;

n is 2 or 3; preferably 2;

t is from 0 to 10; preferably 0; and

x is from 1.5 to 8; preferably 1.5 to 4; more preferably from 1.6 to2.7.

These surfactants are disclosed in U.S. Pat. Nos. 4,565,647, Llenado,issued Jan. 21, 1986; 4,536,318, Cook et al., issued Aug. 20, 1985;4,536,317, Llenado et al., issued Aug. 20, 1985; 4,599,188 Llenado,issued Jul. 8, 1986; and 4,536,319, Payne, issued Aug. 20, 1985; all ofwhich are incorporated herein by reference.

The compositions of the present invention can also comprise mixtures ofthe above nonionic surfactants.

A thorough discussion of nonionic surfactants for detergent bar andliquid products is presented by U.S. Pat. Nos. 5,510,042, Hartman etal., and 4,483,779, Llenado, et al., incorporated herein by reference.

B. Anionic Surfactants

Anionic surfactants include any of the known hydrophobes attached to acarboxylate, sulfonate, sulfate or phosphate polar, solubilizing groupincluding salts. Salts may be the sodium, potassium, ammonium and aminesalts of such surfactants. Useful anionic surfactants can be organicsulfuric reaction products having in their molecular structure an alkylgroup containing from about 8 to about 22 carbon atoms and a sulfonicacid or sulfuric acid ester group, or mixtures thereof. (Included in theterm “alkyl” is the alkyl portion of acyl groups.) Examples of thisgroup of synthetic detersive surfactants which can be used in thepresent invention are the alkyl sulfates, especially those obtained bysulfating the higher alcohols (C₈-C₁₈ carbon atoms) produced from theglycerides of tallow or coconut oil; and alkyl benzene sulfonates.

Other useful anionic surfactants herein include the esters ofalpha-sulfonated fatty acids preferably containing from about 6 to 20carbon atoms in the ester group; 2-acyloxyalkane-1-sulfonic acidspreferably containing from about 2 to 9 carbon atoms in the acyl groupand from about 9 to about 23 carbon atoms in the alkane moiety; alkylether sulfates preferably containing from about 10 to 20 carbon atoms inthe alkyl group and from about 1 to 30 moles of ethylene oxide; olefinsulfonates preferably containing from about 12 to 24 carbon atoms; andbeta-alkyloxy alkane sulfonates preferably containing from about 1 to 3carbon atoms in the alkyl group and from about 8 to 20 carbon atoms inthe alkane moiety.

Anionic surfactants based on the higher fatty acids, i.e., “soaps” areuseful anionic surfactants herein. Higher fatty acids containing fromabout 8 to about 24 carbon atoms and preferably from about 10 to about20 carbon atoms and the coconut and tallow soaps can also be used hereinas corrosion inhibitors.

Preferred water-soluble anionic organic surfactants herein includelinear alkyl benzene sulfonates containing from about 10 to about 18carbon atoms in the alkyl group; branched alkyl benzene sulfonatescontaining from about 10 to about 18 carbon atoms in the alkyl group;the tallow range alkyl sulfates; the coconut range alkyl glycerylsulfonates; alkyl ether (ethoxylated) sulfates wherein the alkyl moietycontains from about 12 to 18 carbon atoms and wherein the average degreeof ethoxylation varies between 1 and 12, especially 3 to 9; the sulfatedcondensation products of tallow alcohol with from about 3 to 12,especially 6 to 9, moles of ethylene oxide; and olefin sulfonatescontaining from about 14 to 16 carbon atoms.

Specific preferred anionics for use herein include: the linear C₁₀-C₁₄alkyl benzene sulfonates (LAS); the branched C₁₀-C₁₄ alkyl benzenesulfonates (ABS); the tallow alkyl sulfates, the coconut alkyl glycerylether sulfonates; the sulfated condensation products of mixed C₁₀-C₁₈tallow alcohols with from about 1 to about 14 moles of ethylene oxide;and the mixtures of higher fatty acids containing from 10 to 18 carbonatoms.

It is to be recognized that any of the foregoing anionic surfactants canbe used separately herein or as mixtures. Moreover, commercial grades ofthe surfactants can contain non-interfering components which areprocessing by-products. For example, commercial alkaryl sulfonates,preferably C₁₀-C₁₄, can comprise alkyl benzene sulfonates, alkyl toluenesulfonates, alkyl naphthalene sulfonates and alkyl poly-benzenoidsulfonates. Such materials and mixtures thereof are fully contemplatedfor use herein.

Other examples of the anionic surfactants used herein include fatty acidsoaps, ether carboxylic acids and salts thereof, alkane sulfonate salts,α-olefin sulfonate salts, sulfonate salts of higher fatty acid esters,higher alcohol sulfate ester or ether ester salts, alkyl, preferablyhigher alcohol phosphate ester and ether ester salts, and condensates ofhigher fatty acids and amino acids.

Fatty acid soaps include those having the formula: R—C(O)OM, wherein Ris C₆ to C₂₂ alkyl and M is preferably sodium.

Salts of ether carboxylic acids and salts thereof include those havingthe formula: R—(OR¹)_(n)—OCH₂C(O)OM, wherein R is C₆ to C₂₂ alkyl, R¹ isC₂ to C₁₀, preferably C₂ alkyl, and M is preferably sodium.

Alkane sulfonate salts and α-olefin sulfonate salts have the formula:R—SO₃M, wherein R is C₆ to C₂₂ alkyl or α-olefin, respectively, and M ispreferably sodium.

Sulfonate salts of higher fatty acid esters include those having theformula:

RC(O)O—R¹—SO₃M,

wherein R is C₁₂ to C₂₂ alkyl, R¹ is C₁ to C₁₈ alkyl and M is preferablysodium.

Higher alcohol sulfate ester salts include those having the formula:RC(O)O—R¹—OSO₃M,

wherein R is C₁₂-C₂₂ alkyl, R¹ is C₁-C₁₈ hydroxyalkyl, M is preferablysodium.

Higher alcohol sulfate ether ester salts include those having theformula:

RC(O)(OCH₂CH₂), —R¹—OSO₃M,

wherein R is C₁₂-C₂₂ alkyl, R¹ is C₁-C₁₈ hydroxyalkyl, M is preferablysodium and x is an integer from 5 to 25.

Higher alcohol phosphate ester and ether ester salts include compoundsof the formulas:

R—(OR¹)_(n)—OPO(OH)(OM);

(R—(OR¹)_(n)—O)₂PO(OM); and

(R—(OR¹)_(n)—O)₃—PO,

wherein R is alkyl or hydroxyalkyl of 12 to 22 carbon atoms, R¹ is C₂H₄,n is an integer from 5 to 25, and M is preferably sodium.

Other anionic surfactants herein are sodium coconut oil fatty acidmonoglyceride sulfonates and sulfates; sodium or potassium salts ofalkyl phenol ethylene oxide ether sulfates containing from about 1 toabout 10 units of ethylene oxide per molecule and wherein the alkylgroups contain from about 8 to about 12 carbon atoms; and sodium orpotassium salts of alkyl ethylene oxide ether sulfates containing about1 to about 10 units of ethylene oxide per molecule and wherein the alkylgroup contains from about 10 to about 20 carbon atoms.

C. Cationic Surfactants

Preferred cationic surfactants of the present invention are the reactionproducts of higher fatty acids with a polyamine selected from the groupconsisting of hydroxyalkylalkylenediamines and dialkylenetriamines andmixtures thereof.

A preferred component is a nitrogenous compound selected from the groupconsisting of:

-   -   (i) the reaction product mixtures of higher fatty acids with        hydroxyalkylalkylenediamines in a molecular ratio of about 2:1,        said reaction product containing a composition having a compound        of the formula:

-   -    wherein R₁ is an acyclic aliphatic C₁₅-C₂₁ hydrocarbon group        and R₂ and R₃ are divalent C₁-C₃ alkylene groups; commercially        available as Mazamide 6 from PPG;    -   (ii) the reaction product of higher fatty acids with        dialkylenetriamines in a molecular ratio of about 2:1; said        reaction product containing a composition having a compound of        the formula:

-   -    wherein R₁, R₂ and R₃ are as defined above; and mixtures        thereof.

Another preferred component is a cationic nitrogenous salt containingone long chain acyclic aliphatic C₁₅-C₂₂ hydrocarbon group selected fromthe group consisting of:

-   -   (i) acyclic quaternary ammonium salts having the formula:

-   -    wherein R₄ is an acyclic aliphatic C₁₅-C₂₂ hydrocarbon group,        R₅ and R₆ are C₁-C₄ saturated alkyl or hydroxyalkyl groups, and        A[−] is an anion, especially as described in more detail        hereinafter, examples of these surfactants are sold by Sherex        Chemical Company under the Adgen trademarks;    -   (ii) substituted imidazolinium salts having the formula:

-   -    wherein R₁ is an acyclic aliphatic C₁₅-C₂₁ hydrocarbon group,        R₇ is a hydrogen or a C₁-C₄ saturated alkyl or hydroxyalkyl        group, and A [−] is an anion;    -   (iii) substituted imidazolinium salts having the formula:

-   -    wherein R₂ is a divalent C₁-C₃ alkylene group and R₁, R₅ and A        [−] are as defined above; an example of which is commercially        available under the Monaquat ISIES trademark from Mona        Industries, Inc.;    -   (iv) alkylpyridinium salts having the formula:

-   -    wherein R₄ is an acyclic aliphatic C₁₆-C₂₂ hydrocarbon group        and A [−] is an anion; and    -   (v) alkanamide alkylene pyridinium salts having the formula:

-   -    wherein R₁ is an acyclic aliphatic C₁₅-C₂₁ hydrocarbon group,        R₂ is a divalent C₁-C₃ alkylene group, and A [−] is an ion        group; and mixtures thereof.

Another class of preferred cationic nitrogenous salts having two or morelong chain acyclic aliphatic C₁₅-C₂₂ hydrocarbon groups or one saidgroup and an arylalkyl group are selected from the group consisting of:

-   -   (i) acyclic quaternary ammonium salts having the formula:

-   -    wherein each R₄ is an acyclic aliphatic C₁₅-C₂₂ hydrocarbon        group, R₅ is a C₁-C₄ saturated alkyl or hydroxyalkyl group, R₈        is selected from the group consisting of R₄ and R₅ groups, and A        [−] is an anion defined as above; examples of which are        commercially available from Sherex Company under the Adgen        trademarks;    -   (ii) diamido quaternary ammonium salts having the formula:

-   -    wherein each R₁ is an acyclic aliphatic C₁₅-C₂₁ hydrocarbon        group, R₂ is a divalent alkylene group having 1 to 3 carbon        atoms, R₅ and R₉ are C₁-C₄ saturated alkyl or hydroxyalkyl        groups, and A [−] is an anion; examples of which are sold by        Sherex Chemical Company under the Varisoft trademark;    -   (iii) diamino alkoxylated quaternary ammonium salts having the        formula:

-   -    wherein n is equal to 1 to about 5, and R₁, R₂, R₅ and A [−]        are as defined above;    -   (iv) quaternary ammonium compounds having the formula:

-   -    wherein each R₄ is an acyclic aliphatic C₁₅-C₂₂ hydrocarbon        group, each R₅ is a C₁-C₄ saturated alkyl or hydroxyalkyl group,        and A [−] is an anion; examples of such surfactants are        available from Onyx Chemical Company under the Ammonyx® 490        trademark;    -   (v) substituted imidazolinium salts having the formula:

-   -    wherein each R₁ is an acyclic aliphatic C₁₅-C₂₁ hydrocarbon        group, R₂ is a divalent alkylene group having 1 to 3 carbon        atoms, and R₅ and A [−] are as defined above; examples are        commercially available from Sherex Chemical Company under the        Varisoft 475 and Varisoft 445 trademarks; and    -   (vi) substituted imidazolinium salts having the formula:

-   -    wherein R₁, R₂ and A − are as defined above; and mixtures        thereof.

The more preferred cationic conventional surfactant is selected from thegroup consisting of an alkyltrimethylammonium salt, adialkyldimethylammonium salt, an alkyldimethylbenzylammonium salt, analkylpyridinium salt, an alkylisoquinolinium salt, benzethoniumchloride, and an acylamino acid cationic surfactant.

Anion A

In the cationic nitrogenous salts herein, the anion A [−] provideselectrical neutrality. Most often, the anion used to provide electricalneutrality in these salts is a halide, such as chloride, bromide, oriodide. However, other anions can be used, such as methylsulfate,ethylsulfate, acetate, formate, sulfate, carbonate, and the like.Chloride and methylsulfate are preferred herein as anion A.

Cationic surfactants are commonly employed as fabric softeners incompositions added during the rinse cycle of clothes washing. Manydifferent types of fabric conditioning agents have been used in rinsecycle added fabric conditioning compositions as disclosed by U.S. Pat.No. 5,236,615, Trinh et al. and U.S. Pat. No. 5,405,542, Trinh et al.,both patents herein incorporated by reference in their entirety. Themost favored type of agent has been the quaternary ammonium compounds.Many such quaternary ammonium compounds are disclosed for example, byU.S. Pat. No. 5,510,042, Hartman et al. incorporated herein by referencein its entirety. These compounds may take the form of noncyclicquaternary ammonium salts having preferably two long chain alkyl groupsattached to the nitrogen atoms. Additionally, imidazolinium salts havebeen used by themselves or in combination with other agents in thetreatment of fabrics as disclosed by U.S. Pat. No. 4,127,489, Pracht, etal., incorporated herein by reference in its entirety. U.S. Pat. No.2,874,074, Johnson discloses using imidazolinium salts to conditionfabrics; and U.S. Pat. No. 3,681,241, Rudy, and U.S. Pat. No. 3,033,704,Sherrill et al. disclose fabric conditioning compositions containingmixtures of imidazolinium salts and other fabric conditioning agents.These patents are incorporated herein by reference in their entirety.

D. Amphoteric Surfactants

Amphoteric surfactants have a positive or negative charge or both on thehydrophilic part of the molecule in acidic or alkaline media.

Examples of the amphoteric surfactants which can be used herein includeamino acid, betaine, sultaine, phosphobetaines, imidazoliniumderivatives, soybean phospholipids, and yolk lecithin Examples ofsuitable amphoteric surfactants include the alkali metal, alkaline earthmetal, ammonium or substituted ammonium salts of alkyl amphocarboxyglycinates and alkyl amphocarboxypropionates, alkyl amphodipropionates,alkyl amphodiacetates, alkyl amphoglycinates and alkyl amphopropionateswherein alkyl represents an alkyl group having 6 to 20 carbon atoms.Other suitable amphoteric surfactants include alkyliminopropionates,alkyl iminodipropionates and alkyl amphopropylsulfonates having between12 and 18 carbon atoms, alkylbetaines and amidopropylbetaines andalkylsultaines and alkylamidopropylhydroxy sultaines wherein alkylrepresents an alkyl group having 6 to 20 carbon atoms are especiallypreferred.

Particularly useful amphoteric surfactants include both mono anddicarboxylates such as those of the formulae:

wherein R is an alkyl group of 6-20 carbon atoms, x is 1 or 2 and M ishydrogen or sodium. Mixtures of the above structures are particularlypreferred.

Other formulae for the above amphoteric surfactants include thefollowing:

where R is an alkyl group of 6-20 carbon atoms and M is hydrogen orsodium.

Of the above amphoteric surfactants, particularly preferred are thealkali salts of alkyl amphocarboxyglycinates and alkylamphocarboxypropionates, alkyl amphodipropionates, alkylamphodiacetates, alkyl amphoglycinates, alkyl amphopropyl sulfonates andalkyl amphopropionates wherein alkyl represents an alkyl group having 6to 20 carbon atoms. Even more preferred are compounds wherein the alkylgroup is derived from coconut oil or is a lauryl group, for example,cocoamphodipropionate. Such cocoamphodipropionate surfactants arecommercially sold under the trademarks Miranol C2M-SF CONC. and MiranolFBS by Rhodia, Inc.

Other commercially useful amphoteric surfactants are available fromRhodia, Inc. and include:

-   -   cocoamphoacetate (sold under the trademarks MIRANOL CM CONC. and        MIRAPON FA),    -   cocoamphopropionate (sold under the trademarks MIRANOL CM-SF        CONC. and MIRAPON FAS),    -   cocoamphodiacetate (sold under the trademarks MIRANOL C2M CONC.        and MIRAPON FB),    -   lauroamphoacetate (sold under the trademarks MIRANOL HM CONC.        and MIRAPON LA),    -   lauroamphodiacetate (sold under the trademarks MIRANOL H2M CONC.        and MIRAPON LB),    -   lauroamphodipropionate (sold under the trademarks MIRANOL H2M SF        CONC. AND MIRAPON LBS),    -   lauroamphodiacetate obtained from a mixture of lauric and        myristic acids (sold under the trademark MIRANOL BM CONC.), and    -   cocoamphopropyl sulfonate (sold under the trademark MIRANOL CS        CONC.)

Somewhat less preferred are:

-   -   caproamphodiacetate (sold under the trademark MIRANOL S2M        CONC.),    -   caproamphoacetate (sold under the trademark MIRANOL SM CONC.),    -   caproamphodipropionate (sold under the trademark MIRANOL KM-SF        CONC.), and    -   stearoamphoacetate (sold under the trademark MIRANOL DM).

E. Gemini Surfactants

Gemini surfactants form a special class of surfactant. These surfactantshave the general formula:

A-G-A¹

and get their name because they comprise two surfactant moieties (A,A¹)joined by a spacer (G), wherein each surfactant moiety (A,A,¹) has ahydrophilic group and a hydrophobic group. Generally, the two surfactantmoieties (A,A¹) are twins, but they can be different.

The gemini surfactants are advantageous because they have low criticalmicelle concentrations (cmc) and, thus, lower the cmc of solutionscontaining both a gemini surfactant and a conventional surfactant. Lowercmc causes better solubilization and increased detergency at lowersurfactant use levels and unexpectedly enhances the deposition of thesoil release polymers as claimed by this invention with demonstratedresults to follow herein. Soil removal agents adhere to the fabric beinglaundered, much better than when mixed with only non-gemini,conventional surfactants.

Also, the gemini surfactants result in a low pC₂₀ value and low Krafftpoints. The pC₂₀ value is a measure of the surfactant concentration inthe solution phase that will reduce the surface tension of the solventby 20 dynes/cm. It is a measure of the tendency of the surfactant toadsorb at the surface of the solution. The Krafft point is thetemperature at which the surfactant's solubility equals the cmc. LowKrafft points imply better solubility in water, and lead to greaterlatitude in making formulations.

A number of the gemini surfactants are reported in the literature, seefor example, Okahara et al., J. Japan Oil Chem. Soc. 746 (Yukagaku)(1989); Zhu et al., 67 JAOCS 7,459 (July 1990); Zhu et al., 68 JAOCS7,539 (1991); Menger et al., J. Am. Chemical Soc. 113, 1451 (1991);Masuyama et al., 41 J. Japan Chem. Soc. 4,301 (1992); Zhu et al., 69JAOCS 1,30 (January 1992); Zhu et al., 69 JAOCS 7,626 July 1992); Mengeret al., 115 J. Am. Chem. Soc. 2, 10083 (1993); Rosen, Chemtech 30 (March1993); and Gao et al., 71 JAOCS 7,771 (July 1994), all of thisliterature incorporated herein by reference.

Also, gemini surfactants are disclosed by U.S. Pat. Nos. 2,374,354,Kaplan; 2,524,218, Bersworth; 2,530,147 Bersworth (two hydrophobic tailsand three hydrophilic heads); 3,244,724, Guttmann; 5,160,450, Okahara,et al., all of which are incorporated herein by reference.

The gemini surfactants may be anionic, nonionic, cationic or amphoteric.The hydrophilic and hydrophobic groups of each surfactant moiety (A,A¹)may be any of those known to be used in conventional surfactants havingone hydrophilic group and one hydrophobic group.

For example, a typical nonionic gemini surfactant, e.g., abis-polyoxyethylene alkyl ether, would contain two polyoxyethylene alkylether moieties.

Each moiety would contain a hydrophilic group, e.g., polyethylene oxide,and a hydrophobic group, e.g., an alkyl chain.

Gemini surfactants specifically useful in the present invention includegemini anionic or nonionic surfactants of the formulae:

wherein Re represents aryl, preferably phenyl.

R₁, R₃, R₄, Y, Z, a and b are as defined above.

More specifically, these compounds comprise:

wherein R₁, R₄, R₅, Z, a, and b are as defined hereinbefore.

The primary hydroxyl group of these surfactants can be readilyphosphated, sulfated or carboxylated by standard techniques.

The compounds included in Formula II can be prepared by a variety ofsynthetic routes. For instance, the compounds of Formula W can beprepared by condensing a monoalkyl phenol with paraformaldehyde in thepresence of an acid catalyst such as acetic acid. The compounds ofFormula V can be synthesized by a Lewis acid catalyzed reaction of analkylphenol with a dicarboxylic acid, e.g., terephthalic acid.

The compounds of Formula II are more fully described in copendingapplication U.S. Ser. No. 60/009,075 filed Dec. 21, 1995, the entiredisclosure of which is incorporated herein by reference.

A class of gemini surfactants that can be used in providing the improvedemulsions which are operable at lower concentrations as disclosed in thepresent invention include a group of amphoteric, and cationic quaternarysurfactants comprising compounds of the formula:

wherein R, t, and Z are as defined hereinbefore. R₁ is as defined beforeand includes the [-(EO)_(a)(PO)_(b)O—]H moiety. R₂ is as defined before,however, D includes the following moieties: —N(R₆)—C(O)—R₅—CH₂O— and—N(R₆)—C(O)—R₅—N(R₆)—R₄—. When t is zero, the compounds are amphotericand when t is 1, the compounds are cationic quaternary compounds. R₃ isselected from the group consisting of a bond, C₁-C₁₀ alkyl, and—R₈-D₁-R₈— wherein D₁, R₅, R₆, a, b, and R₈ are as defined above (exceptR₈ is not —OR₅O—).

Preferably, the compounds of Formula VII comprise:

wherein R, R₂, R₅ and Z are as defined above and n equals a number fromabout 2 to about 10. More particularly, the compounds of Formula VIIcomprise:

wherein R, R₂, R₅, Z, and n are as defined hereinbefore; and mindependently equals a number between about 2 and about 10.

Representative compounds of Formula VII include:

While the compounds of Formulae VII-XII can be prepared by a variety ofsynthetic routes, it has been found that they can be producedparticularly effectively by a process which utilizes a polyaminereactant having at least four amino groups of which two are terminalprimary amines such as triethylene tetramine. These processes are morefully set forth in copending application “Amphoteric Surfactants HavingMultiple Hydrophobic and Hydrophilic Groups”, U.S. Ser. No. 08/292,993filed Aug. 19, 1994, the entire disclosure of which is incorporatedherein by reference.

Another group of gemini surfactants which have been found to provide thelow concentration emulsions of this invention are the cyclic cationicquaternary surfactants of the formula:

wherein R and R₃ are as identified hereinbefore in formula VII; R₉ isindependently a C₁-C₁₀ alkyl or alkylaryl; and X represents a counterionsuch as an anion illustrated by halogen (Cl, Br, and I), alkylsulfatesuch as methyl or ethylsulfate, alkylphosphate such as methylphosphate,and the like.

Preferably, the compounds used in the present invention comprise thoseof Formula XIII in which R₃ is a C₂-C₄ alkyl, most preferably ethyl, R₉is a lower alkyl of from 1 to about 4 carbon atoms, most preferablymethyl; and X is halogen or methylsulfate.

The compounds of Formula XIII can be prepared by a variety of snytheticroutes though it has been found that they can be produced particularlyeffectively by quaternizing a bisimidazoline prepared by a processdisclosed and claimed in copending application “Amphoteric Surfactantshaving Multiple Hydrophobic and Hydrophilic Groups”, U.S. Ser. No.08/292,993 filed Aug. 19, 1994 wherein a polyamine reactant having atleast four amino groups, of which two are terminal primary amine groups,is reacted with an acylating agent such as a carboxylic acid, ester, andthe naturally occurring triglyceride esters thereof or acid chloridesthereof in an amount sufficient to provide at least about 1.8 fatty acidgroups [R₁C(O)—] per polyamine to provide the bisimidazoline.

Also included in the gemini surfactants useful in this invention arethose of the formula:

wherein R₁₃ is a sugar moiety, e.g., a monosaccharide, desaccharide, orpolysaccharide such as glucose; or a polyhydroxy compound such asglycerol; p is independently 0 to 4; R₃ is as defined above in formulaVII; and R₁₄ is a C₁-C₂₂ alkyl or —C(O)R₄ wherein R₄ is as describedabove.

Some of the compounds such as those described above are set forth morefully in U.S. Pat. No. 5,534,197 which description is incorporatedherein by reference.

In the compounds used in the invention, many of the moieties can bederived from natural sources which will generally contain mixtures ofdifferent saturated and unsaturated carbon chain lengths. The naturalsources can be illustrated by coconut oil or similar natural oil sourcessuch as palm kernel oil, palm oil, osya oil, rapeseed oil, castor oil oranimal fat sources such as herring oil and beef tallow. Generally, thefatty acids from natural sources in the form of the fatty acid or thetriglyceride oil can be a mixture of alkyl radicals containing fromabout 5 to about 22 carbon atoms. Illustrative of the natural fattyacids are caprylic (C₈), capric (C₁₀), lauric (C₁₂), myristic (C₁₄),palmitic (C₁₆), stearic (C₁₈), oleic (C₁₈, monounsaturated), linoleic(C₁₈, diunsaturated), linolenic (C₁₈, triunsaturated), ricinoleic (C₁₈,monounsaturated) arachidic (C₂₀), gadolic (C₂₀, monounsaturated),behenic (C₂₂) and erucic (C₂₂). These fatty acids can be used per se, asconcentrated cuts or as fractionations of natural source acids. Thefatty acids with even numbered carbon chain lengths are given asillustrative though the odd numbered fatty acids can also be used. Inaddition, single carboxylic acids, e.g., lauric acid, or other cuts, assuited for the particular application, may be used.

Where desired, the surfactants used in the present invention can beoxyalkylated by reacting the product with an alkylene oxide according toknown methods, preferably in the presence of an alkaline catalyst. Thefree hydroxyl groups of the alkoxylated derivative can then be sulfated,phosphated or acylated using normal methods such as sulfation withsulfamic acid or sulfur trioxide-pyridine complex, or acylation with anacylating agent such as a carboxylic acid, ester, and the naturallyoccurring triglyceride esters thereof.

For alkylation conditions and commonly used alkylating agents, seeAmphoteric Surfactants Vol. 12, Ed. B. R. Bluestein and C. L. Hilton,Surfactant Science Series 1982, pg. 17 and references cited therein, thedisclosures of which are incorporated herein by reference.

For sulfation and phosphation, see Surfactant Science Series, Vol. 7,Part 1, S. Shore & D. Berger, page 135, the disclosure of which isincorporated herein by reference. For phosphating review, see SurfactantScience Series, Vol. 7, Part II, E. Jungermann & H. Silbertman, page495, the disclosure of which is incorporated herein by reference.

The surfactant compositions of the invention are extremely effective inaqueous solution at low concentrations as defined herein. Thesurfactants of the invention can be used in any amount needed for aparticular application which can be easily determined by a skilledartisan without undue experimentation.

IV. Auxiliary Detergent Ingredients

A. Detergency Builders

Compositions of the present invention may include detergency buildersselected from any of the conventional inorganic and organicwater-soluble builder salts, including neutral or alkaline salts, aswell as various water-insoluble and so-called “seeded” builders.

Builders are preferably selected from the various water-soluble, alkalimetal, ammonium or substituted ammonium phosphates, polyphosphates,phosphonates, polyphosphonates, carbonates, silicates, borates,polyhydroxysulfonates, polyacetates, carboxylates, and polycarboxylates.Most preferred are the alkali metal, especially sodium, salts of theabove.

Specific examples of inorganic phosphate builders are sodium andpotassium tripolyphosphate, pyrophosphate, polymeric metaphate having adegree of polymerization of from about 6 to 21, and orthophosphate.Examples of polyphosphonate builders are the sodium and potassium saltsof ethylene-1,1-diphosphonic acid, the sodium and potassium salts ofethane 1-hydroxy-1,1-diphosphonic acid and the sodium and potassiumsalts of ethane, 1,1,2-triphosphonic acid.

Examples of nonphosphorus, inorganic builders are sodium and potassiumcarbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, andsilicate having a molar ratio of SIO₂ to alkali metal oxide of fromabout 0.5 to about 4.0, preferably from about 1.0 to about 2.4.

Water-soluble, nonphosphorus organic builders useful herein include thevarious alkali metal, ammonium and substituted ammonium polyacetates,carboxylates, polycarboxylates and polyhydroxysulfonates. Examples ofpolyacetate and polycarboxylate builders are the sodium, potassium,lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melliticacid, benzene polycarboxylic acids, and citric acid.

Highly preferred polycarboxylate builders herein are set forth in U.S.Pat. No. 3,308,067, Diehl, issued Mar. 7, 1967 incorporated herein byreference. Such materials include the water-soluble salts of homo- andcopolymers of aliphatic carboxylic acids such as maleic acid, itaconicacid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid andmethylenemalonic acid.

Other builders include the carboxylated carbohydrates of U.S. Pat. No.3,723,322, Diehl incorporated herein by reference.

Other useful builders herein are sodium and potassiumcarboxymethyloxymalonate, carboxymethyloxysuccinate,cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylatephloroglucinol trisulfonate, water-soluble polyacrylates (havingmolecular weights of from about 2,000 to about 200,000 for example), andthe copolymers of maleic anhydride with vinyl methyl ether or ethylene.

Other suitable polycarboxylates for use herein are the polyacetalcarboxylates described in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979to Crutchfield et al.; and U.S. Pat. No. 4,246,495, issued Mar. 27, 1979to Crutchfield et al., both incorporated herein by reference.

“Insoluble” builders include both seeded builders such as 3:1 weightmixtures of sodium carbonate and calcium carbonate; and 2.7:1 weightmixtures of sodium sesquicarbonate and calcium carbonate. Amphorus andcrystalline alumino silicates such as hydrated sodium Zeolite A arecommonly used in laundry detergent applications. They have a particlesize diameter of 0.1 micron to about 10 microns depending on watercontent of these molecules. These are referred to as ion exchangematerials. Crystalline alumino silicates are characterized by theircalcium ion exchange capacity. Amphorus alumino silicates are usuallycharacterized by their magnesium exchange capacity. They can benaturally occurring or synthetically derived.

A detailed listing of suitable detergency builders can be found in U.S.Pat. No. 3,936,537, supra, incorporated herein by reference.

B. Miscellaneous Detergent Ingredients

Detergent composition components may also include hydrotropes, enzymes(e.g., proteases, amylases and cellulases), enzyme stabilizing agents,pH adjusting agents (monoethanolamine, sodium carbonate, etc.) halogenbleaches (e.g., sodium and potassium dichloroisocyanurates), peroxyacidbleaches (e.g., diperoxydodecane-1,12-dioic acid), inorganic percompoundbleaches (e.g., sodium perborate), antioxidants as optional stabilizers,reductive agents, activators for percompound bleaches (e.g.,tetraacetylethylenediamine and sodium nonanoyloxybenzene sulfonate),soil suspending agents (e.g., sodium carboxymethyl cellulose), soilanti-redisposition agents, corrosion inhibitors, perfumes and dyes,buffers, whitening agents, solvents (e.g., glycols and aliphaticalcohols) and optical brighteners. Any of other commonly used auxiliaryadditives such as inorganic salts and common salt, humectants,solubilizing agents, UV absorbers, softeners, chelating agents, staticcontrol agents and viscosity modifiers may be added to the detergentcompositions of the invention.

For bar compositions, processing aids are optionally used such as saltsand/or low molecular weight alcohols such as monodihydric, dihydric(glycol, etc.), trihydric (glycerol, etc.), and polyhydric (polyols)alcohols. Bar compositions may also include insoluble particulatematerial components, referred to as “fillers” such as calcium carbonate,silica and the like.

V. Composition Concentrations

The amount of the aminosilicone compound used in the laundry detergentcompositions and methods of this invention will typically be sufficientto yield a concentration of aminosilicone compound in the washing mediumof from about 0.001 to about 0.2 grams of aminosilicone compound perliter of washing medium, more typically from about 0.005 to about 0.1g/L, and even more typically from about 0.01 to about 0.04 g/L.

In the compositions of the invention, the aminosilicone compound willtypically be present in an amount of from about 0.005 to about 30% byweight, more typically from about 1 to about 10% by weight.

The compositions can be in any form that is convenient for use as adetergent, e.g. bars, powders, flakes, pastes, or liquids which may beaqueous or non-aqueous and structured or unstructured. The detergentcompositions can be prepared in any manner which is convenient andappropriate to the desired physical form so as co-agglomeration, spraydrying, or dispersing in a liquid.

The total weight percentages of the conventional surfactants of thepresent invention, all weight percentages being based on the totalactive weight of the compositions of this invention consisting ofaminosilicone compound, optional carrier, conventional surfactant(s),gemini surfactant(s), soil release agent(s), and (optionally) detergencybuilder(s) are about 10 to about 99.9 weight percent, typically about15-75 weight percent.

The gemini surfactants are typically present, if employed, at a level ofabout 0.005 to about 50, typically from about 0.02-15.0, active weightpercent of the composition.

The polymeric soil release agents, are typically present, if employed,at a level of from about 0.05 to about 40, typically from about 0.2-15active weight percent.

The optional detergency builders are suitably present at a level of fromabout 0 to about 70 weight percent, typically from about 5 to about 50weight percent.

VI. Industrial Applicability

The compositions and methods of this invention can be used to cleanvarious fabrics, e.g. wool, cotton, silk, polyesters, nylon, othersynthetics, blends of multiple synthetics and or synthetic/natural fiberblends. The compositions and method are particularly useful with coloredfabrics, i.e. those that have a visually perceptible hue. Thecompositions and methods are also particularly useful in connection withwashing media that also contain a fragrance. The fragrance need not bepre-mixed or pre-reacted with the aminosilicone oil in any way nor mustthe fragrance as an active principle a hydroxy functional compound.

The fragrance substances that may be used in the context of theinvention include natural and synthetic fragrances, perfumes, scents,and essences and any other substances and mixtures of liquids and/orpowdery compositions which emit a fragrance. As the natural fragrances,there are those of animal origin, such as musk, civet, castreum,ambergris, or the like, and those of vegetable origin, such as lemonoil, rose oil, citronella oil, sandalwood oil, peppermint oil, cinnamonoil, or the like. As synthetic fragrances, there are mixed fragrances ofalpha-pinene, limonene, geraniol, linalool, lavandulol, nerolidol, orthe like.

VII. Soluble Powder Detergent Compositions without Inorganic Phosphates

For a good implementation of the invention, said compositions comprise:

-   -   from 5 to 60%, preferably from 8 to 40%, of their weight of at        least one surface-active agent (S)    -   from 5 to 80%, preferably from 8 to 40%, of their weight of at        least one soluble inorganic or organic builder (B)    -   from 0.01 to 8%, preferably from 0.1 to 5%, very particularly        from 0.3 to 3%, of their weight of at least one aminosilicone        (AS).

Mention may be made, among surface-active agents, of the anionic ornon-ionic surface-active agents commonly used in the field of detergentsfor washing laundry.

Anionic Surface-Active Agents:

Typical anionic surface active agents include the following:

-   -   alkyl ester sulphonates of formula R—CH(SO₃M)-COOR′, where R        represents a C₈₋₂₀, preferably C₁₀-C₁₆, alkyl radical, R′ a        C₁-C₆, preferably C₁-C₃, alkyl radical and M an alkali metal        (sodium, potassium or lithium) cation, a substituted or        unsubstituted ammonium (methyl-, dimethyl-, trimethyl- or        tetramethylammonium, dimethylpiperidinium, and the like) cation        or a cation derived from an alkanolamine (monoethanolamine,        diethanolamine, triethanolamine, and the like);    -   alkyl sulphates of formula ROSO₃M, where R represents a C₅-C₂₄,        preferably C₁₀-C₁₈, alkyl or hydroxyalkyl radical, M        representing a hydrogen atom or a cation with the same        definition as above, and their ethoxylated (EO) and/or        propoxylated (PO) derivatives exhibiting an average of 0.5 to        30, preferably of 0.5 to 10, E0 and/or PO units;    -   alkylamide sulphates of formula RCONHR′OSO₃M, where R represents        a C₂-C₂₂, preferably C₆-C₂₀, alkyl radical, R′ a C₂-C₃ alkyl        radical, M representing a hydrogen atom or a cation with the        same definition as above, and their ethoxylated (EO) and/or        propoxylated (PO) derivatives exhibiting an average of 0.5 to 60        EO and/or PO units;    -   salts of C₈-C₂₄, preferably C₁₄-C₂₀, saturated or unsaturated        fatty acids, C₉-C₂₀ alkylbenzenesulphonates, primary or        secondary C₈-C₂₂ alkylsulphonates, alkylglycerol sulphonates,        the sulphonated polycarboxylic acids described in        GB-A-1,082,179, paraffin sulphonates, N-acyl-N-alkyltaurates,        alkyl phosphates, isethionates, alkylsuccinamates,        alkylsulphosuccinates, the monoesters or diesters of        sulphosuccinates, N-acylsarcosinates, alkylglycoside sulphates        or polyethoxycarboxylates the cation being an alkali metal        (sodium, potassium or lithium), a substituted or unsubstituted        ammonium residue (methyl-, dimethyl-, trimethyl- or        tetramethylammonium, dimethylpiperidinium, and the like), or a        residue derived from an alkanolamine (monoethanolamine,        diethanolamine, triethanolamine, and the like);    -   sophorolipids, such as those in acid or lactone form,        derivatives of 17-hydroxyoctadecenic acid; and the like.

Non-Ionic Surface-Active Agents

Typical non-ionic surface active agents include the following:

-   -   polyoxyalkylenated (polyoxyethylenated, polyoxypropylenated or        polyoxybutylenated) alkylphenols, the alkyl substituent of which        is C₆-C₁₂, containing from 5 to 25 oxyalkylene units; mention        may be made, by way of example, of Triton X-45, X-114, X-100 or        X-102, sold by Rohm & Haas Co., or Igepal NP2 to NP17 from        Rhone-Poulenc;    -   polyoxyalkylenated C₈-C₂₂ aliphatic alcohols containing from 1        to 25 oxyalkylene (oxyethylene or oxypropylene) units; mention        may be made, by way of example, of Tergitol 15-S-9 or Tergitol        24-L-6 NMW, sold by Union Carbide Corp., Neodol 45-9, Neodol        23-65, Neodol 45-7 or Neodol 45-4, sold by Shell Chemical Co.,        Kyro EOB, sold by The Procter & Gamble Co., Synperonic A3 to A9        from ICI, or Rhodasurf IT, DB and B from Rhone-Poulenc;    -   the products resulting from the condensation of ethylene oxide        or of propylene oxide with propylene glycol or ethylene glycol,        with a weight-average molecular mass of the order of 2000 to        10,000, such as the Pluronics sold by BASF;    -   the products resulting from the condensation of ethylene oxide        or of propylene oxide with ethylenediamine, such as the        Tetronics sold by BASF;    -   ethoxylated and/or propoxylated C₈-C₁₈ fatty acids containing        from 5 to 25 oxyethylene and/or oxypropylene units;    -   C₈-C₂₀ fatty acid amides containing from 5 to 30 oxyethylene        units;    -   ethoxylated amines containing from 5 to 30 oxyethylene units;    -   alkoxylated amidoamines containing from 1 to 50, preferably from        1 to 25, very particularly from 2 to 20, oxyalkylene units        (preferably oxyethylene units);    -   amine oxides, such as (C₁₀-C₁₈ alkyl)dimethylamine oxides or        (C₈-C₂₂ alkoxy)ethyldihydroxyethylamine oxides;    -   alkoxylated terpene hydrocarbons, such as ethoxylated and/or        propoxylated a- or b-pinenes, containing from 1 to 30        oxyethylene and/or oxypropylene units;    -   the alkylpolyglycosides which can be obtained by condensation        (for example by acid catalysis) of glucose with primary fatty        alcohols (U.S. Pat. No. 3,598,865, U.S. Pat. No. 4,565,647,        EP-A-132,043, EP-A-132,046, and the like) exhibiting a C₄-C₂₀,        preferably C₈-C₁₈, alkyl group and a mean number of glucose        units of the order of 0.5 to 3, preferably of the order of 1.1        to 1.8, per mole of alkylpolyglycoside (APG); mention may in        particular be made of those exhibiting:    -   a C₈-C₁₄ alkyl group and, on average, 1.4 glucose units per mole    -   a C₁₂-C₁₄ alkyl group and, on average, 1.4 glucose units per        mole    -   a C₈-C₁₄ alkyl group and, on average, 1.5 glucose units per mole    -   a C₈-C₁₀ alkyl group and, on average, 1.6 glucose units per mole        sold respectively under the names Glucopon 600 EC®, Glucopon 600        CSUP®, Glucopon 650 EC® and Glucopon 225 CSUP® by Henkel.

Mention may particularly be made, among soluble inorganic builders (B),of:

-   -   amorphous or crystalline alkali metal silicates of formula        xSiO₂.M₂O.yH₂O, with 1≦x≦3.5 and 0≦y/(x+1+y)≦0.5, where M is an        alkali metal and very particularly sodium, including lamellar        alkali metal silicates, such as those described in U.S. Pat. No.        4,664,839;    -   alkaline carbonates (bicarbonates, sesquicarbonates);    -   cogranules of hydrated alkali metal silicates and of alkali        metal carbonates (sodium or potassium) which are rich in silicon        atoms in the Q2 or Q3 form, described in EP-A-488,868; and    -   tetraborates or borate precursors.

Mention may particularly be made, among soluble organic builders (B),of:

-   -   water-soluble polyphosphonates        (ethane-1-hydroxy-1,1-diphosphonates, salts of        methylenediphosphonates, and the like);    -   water-soluble salts of carboxyl polymers or copolymers, such as        the water-soluble salts of polycarboxylic acids with a molecular        mass of the order of 2000 to 100,000 obtained by polymerization        or copolymerization of ethylenically unsaturated carboxylic        acids, such as acrylic acid, maleic acid or anhydride, fumaric        acid, itaconic acid, mesaconic acid, citraconic acid or        methylenemalonic acid, and very particularly polyacrylates with        a molecular mass of the order of 2000 to 10,000 (U.S. Pat. No.        3,308,067) or copolymers of acrylic acid and of maleic anhydride        with a molecular mass of the order of 5000 to 75,000        (EP-A-066,915);    -   polycarboxylate ethers (oxydisuccinic acid and its salts,        tartrate monosuccinic acid and its salts, tartrate disuccinic        acid and its salts);    -   hydroxypolycarboxylate ethers;    -   citric acid and its salts, mellitic acid, succinic acid and        their salts;    -   salts of polyacetic acids (ethylenediaminetetraacetates,        nitrilotriacetates, N-(2-hydroxyethyl)nitrilodiacetates);    -   (C₅-C₂₀ alkyl)succinic acids and their salts        (2-dodecenylsuccinates, laurylsuccinates, and the like);    -   polyacetal carboxylic esters;    -   polyaspartic acid, polyglutamic acid and their salts;    -   polyimides derived from the polycondensation of aspartic acid        and/or of glutamic acid;    -   polycarboxymethylated derivatives of glutamic acid (such as        N,N-bis(carboxymethyl)glutamic acid and its salts, in particular        the sodium salt) or of other amino acids; and    -   aminophosphonates, such as nitrilotris(methylenephosphonate)s.

For a good implementation of the invention, the said aminosilicone (AS)can be chosen from the aminopolyorganosiloxanes (APS) comprisingsiloxane units of general formulae:

R¹ _(a)B_(b)SiO_((4-a-b)/2)  (I),

where a+b=3, with a=0, 1, 2 or 3 and b=0, 1, 2 or 3

R¹ _(c)A_(d)SiO_((4-c-d)/2)  (II),

where c+d=2, with c=0 or 1 and d=1 or 2

R¹ ₂SiO_(2/2)  (III) and optionally

R¹ _(e)A_(f)SiO_((4-e-f)/2)  (IV),

where e+f=0 or 1, with e=0 or 1 and f=0 or 1 in which formulae,

-   -   the R¹ symbols, which are identical or different, represent a        saturated or unsaturated, linear or branched, aliphatic radical        containing from 1 to 10 carbon atoms or a phenyl radical,        optionally substituted by fluoro or cyano groups;    -   the A symbols, which are identical or different, represent a        primary, secondary, tertiary or quaternized amino group bonded        to the silicon via an SiC bond;    -   the B symbols, which are identical or different, represent    -   an OH functional group;    -   an OR functional group, where R represents an alkyl group        containing from 1 to 12 carbon atoms, preferably from 3 to 6        carbon atoms, very particularly 4 carbon atoms;    -   an OCOR′ functional group, where R′ represents an alkyl group        containing from 1 to 12 carbon atoms, preferably 1 carbon atom;        or    -   the A symbol.

The aminopolyorganosiloxanes (APS) preferably comprise units of formula(I), (II), (III) and optionally (IV), where

-   -   in the units of formula (I), a=1, 2 or 3 and b=0 or 1 and    -   in the units of formula (II), c=1 and d=1.

The A symbol is preferably an amino group of formula

—R²—N(R³)(R⁴)

where

-   -   the R² symbol represents an alkylene group containing from 2 to        6 carbon atoms, which group is optionally substituted or        interrupted by one or more nitrogen or oxygen atoms,    -   the R³ and R⁴ symbols, which are identical or different,        represent    -   H,    -   an alkyl or hydroxyalkyl group containing from 1 to 12 carbon        atoms, preferably from 1 to 6 carbon atoms,    -   an aminoalkyl group, preferably a primary aminoalkyl group, the        alkyl group of which contains from 1 to 12 carbon atoms,        preferably from 1 to 6 carbon atoms, which group is optionally        substituted and/or interrupted by at least one nitrogen and/or        oxygen atom, the said amino group optionally being quaternized,        for example by a hydrohalic acid or an alkyl or aryl halide.

Mention may particularly be made, as example of A symbol, of those offormulae:

—(CH₂)₃NH₂; —(CH₂)₃NH₃ ⁺X⁻;

—(CH₂)₃N(CH₃)₂; —(CH₂)₃N⁺(CH₃)₂(C₁₈H₃₇) X⁻;

—(CH₂)₃NHCH₂CH₂NH₂; —(CH₂)₃N(CH₂CH₂OH)₂; and

—(CH₂)₃N(CH₂CH₂NH₂)₂.

Among these, the preferred formulae are:

—(CH₂)₃NH₂—(CH₂)₃NHCH₂CH₂NH₂ and —(CH₂)₃N(CH₂CH₂NH₂)₂.

The R¹ symbol preferably represent methyl, ethyl, vinyl, phenyl,trifluoropropyl or cyanopropyl groups. It very particularly representsthe methyl group (at least predominantly).

The B symbol preferably represents an OR group where R contains from 1to 6 carbon atoms, very particularly 4 carbon atoms, or the A symbol.The B symbol is very preferably a methyl or butoxy group.

The aminosilicone is preferably at least substantially linear. It isvery preferably linear, that is to say does not contain units of formula(IV). It can exhibit a number-average molecular mass of the order of2000 to 50,000, preferably of the order of 3000 to 30,000.

For a good implementation of the invention, the aminosilicones (AS) orthe aminopolyorganosiloxanes (APS) can exhibit in their chain, per totalof 100 silicon atoms, from 0.1 to 50, preferably from 0.3 to 10, veryparticularly from 0.5 to 5, aminofunctionalized silicon atoms.

Insoluble inorganic builders can additionally be present but in alimited amount, in order not to exceed the level of less than 20% ofinsoluble inorganic material defined above.

Mention may be made, among these adjuvants, of crystalline or amorphousaluminosilicates of alkali metals (sodium or potassium) or of ammonium,such as zeolites A, P, X, and the like.

The detergent compositions can additionally comprise standard additivesfor powder detergent compositions. Typical such additional ingredientsare as follows.

Additional Soil Release Agents

Additional soil release agents may be provided in amounts of the orderof 0.01-10%, preferably of the order of 0.1 to 5% and very particularlyof the order of 0.2-3% by weight. Typical such agents include any of thefollowing:

-   -   cellulose derivatives, such as cellulose hydroxyethers,        methylcellulose, ethylcellulose, hydroxypropyl methylcellulose        or hydroxybutyl methylcellulose;    -   poly(vinyl ester)s grafted onto polyalkylene stems, such as        poly(vinyl acetate)s grafted onto polyoxyethylene stems        (EP-A-219,048);    -   poly(vinyl alcohol)s;    -   polyester copolymers based on ethylene terephthalate and/or        propylene terephthalate and polyoxyethylene terephthalate units,        with an ethylene terephthalate and/or propylene terephthalate        (number of units)/polyoxyethylene terephthalate (number of        units) molar ratio of the order of 1/10 to 10/1, preferably of        the order of 1/1 to 9/1, the polyoxyethylene terephthalates        exhibiting polyoxyethylene units having a molecular weight of        the order of 300 to 5000, preferably of the order of 600 to 5000        (U.S. Pat. No. 3,959,230, U.S. Pat. No. 3,893,929, U.S. Pat. No.        4,116,896, U.S. Pat. No. 4,702,857 and U.S. Pat. No. 4,770,666);    -   sulphonated polyester oligomers, obtained by sulphonation of an        oligomer derived from ethoxylated allyl alcohol, from dimethyl        terephthalate and from 1,2-propanediol, exhibiting from 1 to 4        sulphonate groups (U.S. Pat. No. 4,968,451);    -   polyester copolymers based on propylene terephthalate and        polyoxyethylene terephthalate units which are optionally        sulphonated or carboxylated and terminated by ethyl or methyl        units (U.S. Pat. No. 4,711,730) or optionally sulphonated        polyester oligomers terminated by alkylpolyethoxy groups (U.S.        Pat. No. 4,702,857) or anionic sulphopolyethoxy (U.S. Pat. No.        4,721,580) or sulphoaroyl (U.S. Pat. No. 4,877,896) groups;    -   sulphonated polyesters with a molecular mass of less than        20,000, obtained from a diester of terephthalic acid,        isophthalic acid, a diester of sulphoisophthalic acid and a        diol, in particular ethylene glycol (WO 95/32997);    -   polyesterpolyurethanes obtained by reaction of a polyester with        a number-average molecular mass of 300 to 4000, obtained from        adipic acid and/or terephthalic acid and/or sulphoisophthalic        acid and a diol, with a prepolymer containing end isocyanate        groups obtained from a poly(ethylene glycol) with a molecular        mass of 600-4000 and a diisocyanate (FR-A-2,334,698).

Anti-Redeposition Agents

Anti-redeposition agents may be provided in amounts of approximately0.01-10% by weight for a powder detergent composition and ofapproximately 0.01-5% by weight for a liquid detergent composition.Typical such agents include any of the following:

-   -   ethoxylated monoamines or polyamines or ethoxylated amine        polymers (U.S. Pat. No. 4,597,898, EP-A-011,984);    -   carboxymethylcellulose;    -   sulphonated polyester oligomers obtained by condensation of        isophthalic acid, dimethyl sulphosuccinate and diethylene glycol        (FR-A-2,236,926); and    -   polyvinylpyrrolidones.

Bleaching Agents

Bleaching agents may be provided in an amount of approximately 0.1-20%,preferably 1-10%, of the weight of the said powder detergentcomposition. Typical such agents include any of the following:

-   -   perborates, such as sodium perborate monohydrate or        tetrahydrate;    -   peroxygenated compounds, such as sodium carbonate peroxohydrate,        pyrophosphate peroxohydrate, urea hydrogen peroxide, sodium        peroxide or sodium persulphate;    -   percarboxylic acids and their salts (known as “percarbonates”),        such as magnesium monoperoxyphthalate hexahydrate, magnesium        meta-chloroperbenzoate, 4-nonylamino-4-oxoperoxybutyric acid,        6-nonylamino-6-oxoperoxycaproic acid, diperoxydodecanedioic        acid, peroxysuccinic acid nonylamide or decyldiperoxysuccinic        acid,        preferably in combination with a bleaching activator generating,        in situ in the washing liquor, a peroxycarboxylic acid; mention        may be made, among these activators, of        tetraacetylethylenediamine, tetraacetylmethylenediamine,        tetraacetylglycoluril, sodium p-acetoxybenzenesulphonate,        pentacetylglucose, octaacetyllactose, and the like.

Fluorescence Agents

Fluorescence agetns may be provided in an amount of approximately0.05-1.2% by weight. Typical such agents include any derivatives ofstilbene, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles,methinecyanines, thiophenes, and the like;

Foam-Suppressant Agents

Foam-suppressant agents may be provided in amounts which can range up to5% by weight. Typical such agents include any of the following:

-   -   C₁₀-C₂₄ fatty monocarboxylic acids or their alkali metal,        ammonium or alkanolamine salts or fatty acid triglycerides;    -   saturated or unsaturated, aliphatic, alicyclic, aromatic or        heterocyclic hydrocarbons, such as paraffins or waxes;    -   N-alkylaminotriazines;    -   monostearyl phosphates or monostearyl alcohol phosphates; and    -   polyorganosiloxane oils or resins, optionally combined with        silica particles;

Softeners

Softeners may be provided in amounts of approximately 0.5-10% by weight.Typical such agents are clays (smectites, such as montmorillonite,hectorite or saponite);

Enzymes

Enzymes may be provided in an amount which can range up to 5 mg byweight, preferably of the order of 0.05-3 mg, of active enzyme/g ofdetergent composition. Typical enzymes are proteases, amylases, lipases,cellulases or peroxydases (U.S. Pat. No. 3,553,139, U.S. Pat. No.4,101,457, U.S. Pat. No. 4,507,219 and U.S. Pat. No. 4,261,868).

Other Additives

Typical other additives may be any of the following:

-   -   alcohols (methanol, ethanol, propanol, isopropanol, propanediol,        ethylene glycol or glycerol);    -   buffer agents or fillers, such as sodium sulphate or alkaline        earth metal carbonates or bicarbonates; and    -   pigments,        the amounts of optional insoluble inorganic additives having to        be sufficiently limited in order not to exceed the level of less        than 20% of insoluble inorganic materials defined above.

Agrochemical Foams

The foam enhancers of the present invention may also be employed infoams for delivering agrochemicals, for example, herbicides, pesticides,fungicides, or detoxifying agents. Examples of foams for agrochemicalsare disclosed by U.S. Pat. Nos. 3,960,763 to Lambou, et al; 5,346,699 toTiernan, et al; 5,549,869 to Iwakawa; 5,686,024 to Dahanayake et al; and5,735,955 to Monaghan et al, all of which are incorporated herein byreference in their entirety.

Oil Field Foams

The foam enhancers of the present invention may be employed in foams foruse in subterranean formations, such as oil wells. For example, foamsare employed in drilling fluids, as well as in enhanced oil recoverywith steam or carbon dioxide. Examples of foams for use in oil wells aredisclosed by U.S. Pat. Nos. 5,821,203 to Williamson; 5,706,895 toSydansk; 5,714,001 to Savoly, et al; 5,614,473 to Dino, et al; 5,042,583to D'Souza, et al; and 5,027,898 to Naae, all of which are incorporatedherein by reference in their entirety.

Fire-Fighting Foams

The foam enhancer of the present invention may be employed in foams foruse in fire-fighting. Typical fire-fighting foams are disclosed in U.S.Pat. Nos. 5,882,541 to Achtmann; 5,658,961 to Cox, Sr.; 5,496,475 toJho, et al; 5,218,021 to Clark et al; and 4,713,182 to Hiltz, et al, allof which are incorporated herein by reference in their entirety.

Coagulants for Treating Paper Making Water

The foam enhancers of the present invention also have another useunrelated to foaming. They are retention aids for retention of titaniumdioxide (TiO₂) used for whitening paper during paper making. Theseretention aids act as coagulants to cause particles of titanium dioxideto coagulate. The coagulated particles deposit on the paper. As aresult, water will drain faster from paper upon which coagulatedtitanium dioxide is deposited. The use of titanium dioxide for whiteningpaper is disclosed by U.S. Pat. Nos. 5,665,466 to Guez et al; 5,705,033to Gerard, et al; and 5,169,441 to Lauzon, all of which are incorporatedherein by reference in their entirety.

Hard Surface Cleaners

The foam enhancer of the present invention may be employed with foamhard surface cleaners as are typically employed with bathroom tilesurfaces. Examples of such foam cleaners are disclosed by U.S. Pat. No.5,612,308 to Woo, et al and U.S. Pat. No. 5,232,632 to Woo et al,incorporated herein by reference.

Shower Rinse

The polymers of the present invention are also useful in shower rinsesto make them better maintain a clean shower and prevent buildup ofundesired deposits. Typical shower rinses are disclosed by U.S. Pat.Nos. 5,536,452 to Black and 5,587,022 to Black, incorporated herein byreference.

High Purity Compositions

A particular process may be advantageous to make copolymers from atleast one tertiary amino-containing monomer, e.g.,dimethylaminoethyl(meth)acrylate, and at least one vinyl-containingmonomer, when the at least one vinyl-functional monomer is notsubstituted by an alkyl group on the 2-position of the vinyl moiety (forexample, not methacrylic acid, hydroxyethylmethacrylate orhydroxypropylmethacrylate). This is advantageous to make such copolymersfree of or having minimal Michael addition adducts of the ingredients.Also, Michael addition adducts form but revert back to monomers if thehydrogen atom is substituted by an alkyl group on the 2-position of thevinyl moiety.

In the process, at least one tertiary amino-containing monomer, at leastone vinyl-containing monomer not substituted by an alkyl group on the2-position of the vinyl moiety, an acid, and a polymerization initiatorare mixed in a polymerization reactor to form a polymerization mixturein the reactor. The at least one tertiary amino-containing monomer andthe at least one vinyl-containing monomer are copolymerized in thepolymerization mixture, to form a copolymer, and optionally a Michaeladdition adduct of the at least one tertiary amino-containing monomerand the at least one vinyl-containing monomer. However, Michael adductformation is prevented/minimized by performing at least one of thefollowing steps in a process for making copolymers from tertiary aminomonomers and vinyl-functional monomers:

1. Avoid formation of adduct by separating the tertiary amino monomer(e.g. dimethylaminoethyl(meth)acrylate) from the vinyl-functionalmonomer prior to polymerization.

2. Avoid formation of adduct by maintaining the at least one tertiaryamino-containing monomer and the at least one vinyl-functional monomerwater-free prior to the copolymerizing.

3. Conduct polymerization at a high temperature (typically about 70 toabout 90° C., preferably about 80 to about 90° C.) and at a suitable pH(typically about 3 to about 10, preferably about 4 to about 8, mostpreferably about 4 to about 6) to cause the adduct formed to be unstableand revert to monomers. Thus, monomers bound by the adduct will beliberated to copolymerize.

Typically, the at least one vinyl-functional monomer has is selectedfrom at least one member of the group consisting of a monomer of FormulaA:

wherein R¹⁶ is a group which permits the vinyl-functional monomer toundergo Michael addition.

Preferably, the acid reactants, e.g., mineral acid (for example sulfuricacid) or citric acid, is fed to the reactor before the monomers.Typically these processes are performed as semi-batch processes.However, batch or continuous processes are not precluded.

In a particular embodiment, a tertiary amino-containing monomer, water,and an acid may be mixed in a reactor to form a neutralized tertiaryamino-containing monomer mixture having a pH of about 3 to about 10. Theneutralized tertiary amino-containing monomer mixture, avinyl-functional monomer, water, and an initiator are fed to thereactor. The initiator may be a single ingredient (typically sodiumpersulfate) or a redox system combining an oxidizing component(typically sodium persulfate) and a reducing component (typically sodiummetabisulfite). Water is typically fed directly to the reactor with thevinyl-functional monomer and neutralized tertiary amino-containingmonomer, and/or with other ingredients.

Generally, the neutralized tertiary amino-containing monomer mixture, avinyl-functional monomer/water mixture, and initiator are separately fedto the reactor. Preferably, the neutralized tertiary amino-containingmonomer mixture, the vinyl-functional monomer/water mixture, at least aportion of the initiator are separately, yet simultaneously, fed to thereactor to form the polymerization mixture. The initiator can be asingle organic or inorganic compound or a redox (reduction/oxidation)system of two or more compounds. For example, U.S. Pat. No. 5,863,526,incorporated herein by reference in its entirety, discloses typicalinitiator systems. The polymerization mixture is maintained in thereactor at polymerization conditions including a pH of about 3 to about10, preferably about 4 to about 8, most preferably about 4 to about 6,and a temperature of about 70 to about 90° C., preferably about 80 toabout 90° C., for a time of about 1 to about 3 hours, to form acopolymer and the copolymer product is recovered.

In a second embodiment, water and acid are fed first to the reactor.Then, water-free tertiary amino-containing monomer, water-freevinyl-functional monomer and initiator are separately fed to the reactorto admix with the acid and water in the reactor. In the reactor, themonomers polymerize in the presence of the initiator described above.

Generally, the water is provided with acid and initiator. Thepolymerization mixture is maintained at the above-describedpolymerization conditions to form the copolymer product. Then thecopolymer product is recovered. If desired, the tertiaryamino-containing monomer, the vinyl-functional monomer, and theinitiator are separately, yet simultaneously fed to the reactor.

In a third embodiment the process may be the same as the secondembodiment except that the water-free monomers are mixed to form awater-free mixture prior to being fed to the reactor.

The present invention is further illustrated by the following examplesof polymeric enhancing agents, provided that no observations or otherstatements made therein should be construed to limit the invention,unless otherwise expressly indicated in the claims appended hereto. Allamounts, parts, percentages, and ratios expressed in this specification,including the claims are by weight unless otherwise apparent in context.

Example 1 Preparation of Poly(HEA-co-DMAM-co-AA) (9:3:1) Terpolymer

2-Hydroxyethyl acrylate (25.00 g, 215.3 mmol), 2-(dimethylamino)ethylmethacrylate (11.28 g, 71.8 mmol), acrylic acid (1.71 g, 23.7 mmol),2,2′-azobisisobutyronitrile (0.26 g, 1.6 mmol), 1,4-dioxane (150 ml) and2-propanol (30 ml) are placed into a 500 ml three-necked round-bottomedflask, fitted with a heating mantle, magnetic stirrer, internalthermometer and argon inlet. The mixture is sparged with nitrogen for 30minutes to remove dissolved oxygen. The mixture is heated for 18 hourswith stirring at 65° C. TLC (diethyl ether) indicates consumption ofmonomer. An equal volume of water is added and the mixture isconcentrated under vacuum by rotary evaporation to remove the solvent.Water is added to make a 10% solution and the mixture is lyophilized andthen pulverized in a blender to yield an off-white powder. NMR isconsistent with the desired compound.

Example 2 Preparation of Poly(HPA-co-DMAM-co-AA) (9:3:1) Terpolymer

Hydroxypropyl acrylate (25.00 g, 192.1 mmol), 2-(dimethylamino)ethylmethacrylate (10.07 g, 64.0 mmol), acrylic acid (1.52 g, 21.1 mmol),2,2′-azobisisobutyronitrile (0.23 g, 1.4 mmol), 1,4-dioxane (150 ml) and2-propanol (30 ml) are placed into a 500 ml three-necked round-bottomedflask, fitted with a heating mantle, magnetic stirrer, internalthermometer and argon inlet. The mixture is sparged with nitrogen for 30minutes to remove dissolved oxygen. The mixture is heated for 18 hourswith stirring at 65° C. TLC (diethyl ether) indicates consumption ofmonomer. An equal volume of water is added and the mixture isconcentrated under vacuum by rotary evaporation to remove the solvent.Water is added to make a 10% solution and the mixture is lyophilized andthen pulverized in a blender to yield an off-white powder. NMR isconsistent with the desired compound.

Example 3 Preparation of Poly(HEA-co-DMAM) (3:1) Copolymer

2-Hydroxyethyl acrylate (30.00 g, 258.4 mmol), 2-(dimethylamino)ethylmethacrylate (13.54 g, 86.1 mmol), 2,2′-azobisisobutyronitrile (0.28 g,1.7 mmol), 1,4-dioxane (150 ml) and 2-propanol (30 ml) are placed into a500 ml three-necked round-bottomed flask, fitted with a heating mantle,magnetic stirrer, internal thermometer and argon inlet. The mixture issparged with nitrogen for 30 minutes to remove dissolved oxygen. Themixture is heated for 18 hours with stirring at 65° C. TLC (diethylether) indicates consumption of monomer. An equal volume of water isadded and the mixture is concentrated under vacuum by rotary evaporationto remove the solvent. Water is added to make a 10% solution and themixture is lyophilized and then pulverized in a blender to yield anoff-white powder. NMR is consistent with the desired compound.

Example 4 Preparation of Poly(HEA-co-DMAM-co-AA) (3:9:1) Terpolymer

2-Hydroxyethyl acrylate (5.00 g, 43.1 mmol), 2-(dimethylamino)ethylmethacrylate (20.31 g, 129.2 mmol), acrylic acid (1.02 g, 14.2 mmol),2,2′-azobisisobutyronitrile (0.16 g, 1.0 mmol), 1,4-dioxane (92 ml) and2-propanol (18 ml) are placed into a 250 ml three-necked round-bottomedflask, fitted with a heating mantle, magnetic stirrer, internalthermometer and argon inlet. The mixture is sparged with nitrogen for 30minutes to remove dissolved oxygen. The mixture is heated for 18 hourswith stirring at 65° C. TLC (diethyl ether) indicates consumption ofmonomer. An equal volume of water is added and the mixture isconcentrated under vacuum by rotary evaporation to remove the solvent.Water is added to make a 10% solution and the mixture is lyophilized andthen pulverized in a blender to yield an off-white powder. NMR isconsistent with the desired compound.

Example 5 Preparation of Poly(PEG acrylate-co-DMAM-co-AA) (9:3:1)Terpolymer

Poly(ethylene glycol) acrylate (20.00 g, 41.1 mmol),2-(dimethylamino)ethyl methacrylate (2.15 g, 13.7 mmol), acrylic acid(0.33 g, 4.5 mmol), 2,2′-azobisisobutyronitrile (0.001 g, 0.3 mmol),1,4-dioxane (79 ml) and 2-propanol (16 ml) are placed into a 250 mlthree-necked round-bottomed flask, fitted with a heating mantle,magnetic stirrer, internal thermometer and argon inlet. The mixture issparged with nitrogen for 30 minutes to remove dissolved oxygen. Themixture is heated for 18 hours with stirring at 65° C. TLC (diethylether) indicates consumption of monomer. An equal volume of water isadded and the mixture is concentrated under vacuum by rotary evaporationto remove the solvent. Water is added to make a 10% solution and themixture is lyophilized to yield a viscous yellow oil. Water is added tomake a 10% solution. NMR is consistent with the desired compound.

Example 6 Preparation of Poly(DMAM-co-butylvinylether) (1:1) Copolymer

2-(Dimethylamino)ethyl methacrylate (8.00 g, 50.9 mmol),N-butylvinylether (5.10 g, 50.9 mmol), 2,2′-azobisisobutyronitrile (0.08g, 0.5 mmol), 1,4-dioxane (75 ml) and 2-propanol (15 ml) are placed intoa 250 ml three-necked round-bottomed flask, fitted with a heatingmantle, magnetic stirrer, internal thermometer and argon inlet. Themixture is sparged with nitrogen for 30 minutes to remove dissolvedoxygen. The mixture is heated for 18 hours with stirring at 65° C. TLC(diethyl ether) indicates consumption of monomer. An equal volume oft-butanol is added and the mixture is concentrated under vacuum byrotary evaporation to remove the solvent. t-Butanol is added to make a10% solution and the mixture is lyophilized to yield waxy solid. NMR isconsistent with the desired compound.

Example 7 Preparation of Poly(2-diethylaminoethyl vinylether-co-ethyleneglycol monovinyl ether)

Aluminum chloride (1.0 g, 7.5 mmol) is added to a flask containingbenzene (200 mL). A mixture of 2-diethylaminoethyl vinyl ether (100.24g, 0.70 mol) and ethyleneglycol monovinyl ether (183.25 g, 2.08 mol) isadded gradually so as to keep the reaction mixture at 60°-80° C. Afteraddition is complete, the reaction mixture is heated for 3 h. Thesolvent is removed by rotary evaporation at room temperature and thenstripped by kugelrohr distillation at 60° C. (0.5 mm Hg) for 2 h toyield the polymer.

The following are non-limiting examples of liquid detergent compositionscomprising the polymeric enhancing agents employed as suds boostersaccording to an aspect of the present invention.

TABLE I weight % Ingredients 8 9 10 C₁₂-C₁₅ Alkyl sulphate — 28.0 25.0C₁₂-C₁₃ Alkyl (E_(0.6-3)) sulfate 30 — — C₁₂ Amine oxide 5.0 3.0 7.0C₁₂-C₁₄ Betaine 3.0 — 1.0 C₁₂-C₁₄ Polyhydroxy fatty acid amide — 1.5 —C₁₀ Alcohol Ethoxylate E₉ ¹ 2.0 — 4.0 Diamine ² 1.0 — 7.0 Mg²⁺ (asMgCl₂) 0.25 — — Citrate (cit2K3) 0.25 — — Polymeric suds booster ³ 1.252.6 0.9 Minors and water ⁴ balance balance balance pH of a 10% aqueoussolution 9 10 10 ¹ E₉ Ethoxylated Alcohols as sold by the Shell Oil Co.² 1,3-diaminopentane sold as Dytek EP. ³ Suds Booster according to thepresent invention, preferably a suds booster in accordance with Examples1-7, more preferably poly(HEA-co-DMAM-co-AA) (9:3:1) Terpolymer ofExample 1. ⁴ Includes perfumes, dyes, ethanol, etc.

TABLE II weight % Ingredients 11 12 13 C₁₂-C₁₃ Alkyl (E_(0.6-3)) sulfate— 15.0 10.0 Paraffin sulfonate 20.0 — — Na C₁₂-C₁₃ linear alkylbenzenesulfonate 5.0 15.0 12.0 C₁₂-C₁₄ Betaine 3.0 1.0 — C₁₂-C₁₄ Polyhydroxyfatty acid amide 3.0 — 1.0 C₁₀ Alcohol Ethoxylate E₉ ¹ — — 20.0 Diamine² 1.0 — 7.0 DTPA ³ — 0.2 — Mg²⁺ (as MgCl₂) 1.0 — — Ca²⁺ (asCa(citrate)₂) — 0.5 — Protease ⁴ 0.01 — 0.001 Amylase ⁵ — 0.001 0.001Hydrotrope ⁶ 2.0 1.5 3.0 Polymeric suds booster ⁷ 0.5 3.0 0.5 Minors andwater ⁸ balance balance balance pH of a 10% aqueous solution 9.3 8.5 11¹ E₉ Ethoxylated Alcohols as sold by the Shell Oil Co. ²1,3-bis(methylamino)cyclohexane. ³ Diethylenetriaminepentaacetate. ⁴Suitable protease enzymes include Savinase ®; Maxatase ®; Maxacal ®;Maxapem 15 ®; subtilisin BPN and BPN′; Protease B; Protease A; ProteaseD; Primase ®; Durazym ®; Opticlean ®; and Optimase ®; and Alcalase ®. ⁵Suitable amylase enzymes include Termamyl ®, Fungamyl ®; Duramyl ®;BAN ®, and the amylases as described in WO95/26397 and in co-pendingapplication by Novo Nordisk PCT/DK/96/00056. ⁶ Suitable hydrotropesinclude sodium, potassium, ammonium or water-soluble substitutedammonium salts of toluene sulfonic acid, naphthalene sulfonic acid,cumene sulfonic acid, xylene sulfonic acid. ⁷ Suds Booster according tothe present invention, preferably a suds booster in accordance withExamples 1-7, more preferably poly(HPA-co-DMAM-co-AA) (9:3:1) Terpolymerof Example 2. ⁸ Includes perfumes, dyes, ethanol, etc.

TABLE III weight % Ingredients 14 15 16 17 C₁₂-C₁₅ Alkyl (E₁) sulfate —30.0 — — C₁₂-C₁₅ Alkyl (E_(1.4)) sulfate 30.0 — 27.0 — C₁₂-C₁₅ Alkyl(E_(2.2)) sulfate — — — 15 C₁₂ Amine oxide 5.0 5.0 5.0 3.0 C₁₂-C₁₄Betaine 3.0 3.0 — — C₁₀ Alcohol Ethoxylate E₉ ¹ 2.0 2.0 2.0 2.0 Diamine² 1.0 2.0 4.0 2.0 Mg²⁺ (as MgCl₂) 0.25 0.25 — — Ca²⁺ (as Ca(citrate)₂) —0.4 — — Polymeric suds booster ³ 0.5 1.0 0.75 5.0 Minors and water ⁴balance balance balance balance pH of a 10% aqueous solution 7.4 7.6 7.47.8 ¹ E₉ Ethoxylated Alcohols as sold by the Shell Oil Co. ²1,3-diaminopentane sold as Dytek EP. ³ Suds Booster according to thepresent invention, preferably a suds booster in accordance with Examples1-7, more preferably poly(HEA-co-DMAM) (3:1) Copolymer of Example 3. ⁴Includes perfumes, dyes, ethanol, etc.

TABLE IV weight % Ingredients 18 19 20 C₁₂-C₁₃ Alkyl (E_(0.6-3)) sulfate— 15.0 10.0 Paraffin sulfonate 20.0 — — Na C₁₂-C₁₃ linear alkylbenzenesulfonate 5.0 15.0 12.0 C₁₂-C₁₄ Betaine 3.0 1.0 — C₁₂-C₁₄ Polyhydroxyfatty acid amide 3.0 — 1.0 C₁₀ Alcohol Ethoxylate E₉ ¹ — — 20.0 Diamine² 1.0 — 7.0 Mg²⁺ (as MgCl₂) 1.0 — — Ca²⁺ (as Ca(citrate)₂) — 0.5 —Protease ³ 0.1 — — Amylase ⁴ — 0.02 — Lipase ⁵ — — 0.025 DTPA ⁶ — 0.3 —Citrate (cit2K3) 0.65 — — Polymeric suds booster ⁷ 1.5 2.2 3.0 Minorsand water ⁸ balance balance balance pH of a 10% aqueous solution 9.3 8.511 ¹ E₉ Ethoxylated Alcohols as sold by the Shell Oil Co. ²1,3-bis(methylamino)cyclohexane. ³ Suitable protease enzymes includeSavinase ®; Maxatase ®; Maxacal ®; Maxapem 15 ®; subtilisin BPN andBPN′; Protease B; Protease A; Protease D; Primase ®; Durazym ®;Opticlean ®; and Optimase ®; and Alcalase ®. ⁴ Suitable amylase enzymesinclude Termamyl ®, Fungamyl ®; Duramyl ®; BAN ®, and the amylases asdescribed in WO95/26397 and in co-pending application by Novo NordiskPCT/DK/96/00056. ⁵ Suitable lipase enzymes include Amano-P; M1 Lipase ®;Lipomax ®; Lipolase ®; D96L—lipolytic enzyme variant of the nativelipase derived from Humicola lanuginosa as described in U.S. patentapplication Ser. No. 08/341,826; and the Humicola lanuginosa strain DSM4106 ⁶ Diethylenetriaminepentaacetate. ⁷ Suds Booster according to thepresent invention, preferably a suds booster in accordance with Examples1-7, more preferably poly(HEA-co-DMAM-co-AA) (3:9:1) Terpolymer ofExample 4. ⁸ Includes perfumes, dyes, ethanol, etc.

TABLE V weight % Ingredients 21 22 23 C₁₂-C₁₃ Alkyl (E_(0.6-3)) sulfate— 27.0 — C₁₂-C₁₄ Betaine 2.0 2.0 — C₁₄ Amine oxide 2.0 5.0 7.0 C₁₂-C₁₄Polyhydroxy fatty acid amide 2.0 — — C₁₀ Alcohol Ethoxylate E₉ ¹ 1.0 —2.0 Hydrotrope — — 5.0 Diamine ² 4.0 2.0 5.0 Ca²⁺ (as Ca(citrate)₂) —0.1 0.1 Protease ³ — 0.06 0.1 Amylase ⁴ 0.005 — 0.001 Lipase ⁵ — 0.001 —DTPA ⁶ — 0.1 0.1 Citrate (cit2K3) 0.3 — — Polymeric suds booster ⁷ 0.50.8 2.5 Minors and water ⁸ balance balance balance pH of a 10% aqueoussolution 10 9 9.2 ¹ E₉ Ethoxylated Alcohols as sold by the Shell Oil Co.² 1,3-diaminopentane sold as Dytek EP. ³ Suitable protease enzymesinclude Savinase ®; Maxatase ®; Maxacal ®; Maxapem 15 ®; subtilisin BPNand BPN′; Protease B; Protease A; Protease D; Primase ®; Durazym ®;Opticlean ®; and Optimase ®; and Alcalase ®. ⁴ Suitable amylase enzymesinclude Termamyl ®, Fungamyl ®; Duramyl ®; BAN ®, and the amylases asdescribed in WO95/26397 and in co-pending application by Novo NordiskPCT/DK/96/00056. ⁵ Suitable lipase enzymes include Amano-P; M1 Lipase ®;Lipomax ®; Lipolase ®; D96L—lipolytic enzyme variant of the nativelipase derived from Humicola lanuginosa as described in U.S. patentapplication Ser. No. 08/341,826; and the Humicola lanuginosa strain DSM4106 ⁶ Diethylenetriaminepentaacetate. ⁷ Suds Booster according to thepresent invention, preferably a suds booster in accordance with Examples1-7, more preferably poly(PEG acrylate-co-DMAM-co-AA) (9:3:1) Terpolymerof Example 5. ⁸ Includes perfumes, dyes, ethanol, etc.

TABLE VI weight % Ingredients 24 25 26 C₁₂-C₁₃ Alkyl (E_(1.4)) sulfate33.29 24.0 — C₁₂-C₁₃ Alkyl (E_(0.6)) sulfate — — 26.26 C₁₂-C₁₄Polyhydroxy fatty acid amide 4.2 3.0 1.37 C₁₄ Amine oxide 4.8 2.0 1.73C₁₁ Alcohol Ethoxylate E₉ ¹ 1.0 4.0 4.56 C₁₂-C₁₄ Betaine — 2.0 1.73MgCl₂ 0.72 0.47 0.46 Calcium citrate 0.35 — — Polymeric suds booster ²0.5 1.0 2.0 Minors and water ³ balance balance balance pH of a 10%aqueous solution 7.4 7.8 7.8 ¹ E₉ Ethoxylated Alcohols as sold by theShell Oil Co. ² Suds Booster according to the present invention,preferably a suds booster in accordance with Examples 1-7, morepreferably poly(DMAM-co-butylvinylether) (1:1) Copolymer of Example 6. ³Includes perfumes, dyes, ethanol, etc.

TABLE VII Ingredients 27 28 29 30 31 AE0.6S¹ 28.80 28.80 26.09 26.0926.09 Amine oxide² 7.20 7.20 6.50 6.50 6.50 Citric acid 3.00 — — — —Maleic acid — 2.50 — — — Suds boosting 0.22 0.22 0.20 0.20 0.20 polymer³Sodium Cumene 3.30 3.30 3.50 3.50 3.50 Sulfonate Ethanol 40B 6.50 6.506.50 6.50 6.50 C10E8 — — 3.00 3.00 3.00 C11E9⁴ 3.33 3.33 — — — Diamine⁵0.55 0.55 0.50 0.50 0.50 Perfume 0.31 0.31 — — — Water BAL. BAL. BAL.BAL. BAL. Viscosity (cps 330 330 150 330 650 @ 70 F.) pH @ 10% 9.0 9.08.3 9.0 9.0 ¹C12-13 alkyl ethoxy sulfonate containing an average of 0.6ethoxy groups. ²C₁₂-C₁₄ Amine oxide. ³Suds Booster according to thepresent invention, preferably a suds booster in accordance with Examples1-7, more preferably poly(2-diethylaminoethyl vinylether-co-ethyleneglycol monovinyl ether) of Example 7. ⁴C11 Alkylethoxylated surfactant containing 9 ethoxy groups. ⁵1,3bis(methylamine)-cyclohexane. ⁶C10 Alkyl ethoxylated surfactantcontaining 8 ethoxy groups. ⁷1,3 pentane diamine.

TABLE VIII Ingredients 32 33 34 35 36 AE0.6S¹ 26 26 26 26 26 Amineoxide² 6.5 6.5 7.5 7.5 7.5 Citric acid 3.0 — 2.5 — 3.0 Maleic acid — 2.5— 3.0 — C10E8⁶ 3 3 4.5 4.5 4.5 Diamine⁵ 0.5 0.5 1.25 0 1.25 Diamine⁷ 0 00 1 Suds boosting 0 0.2 0.5 0.5 0.5 polymer³ Sodium cumene 3.5 3.5 2 2 2sulphonate Ethanol 8 8 8 8 8 pH 9 9 9 8 10 ¹C12-13 alkyl ethoxysulfonate containing an average of 0.6 ethoxy groups. ²C₁₂-C₁₄ Amineoxide. ³Suds Booster according to the present invention, preferably asuds booster in accordance with Examples 1-7, more preferablypoly(HEA-co-DMAM-co-AA) (3:9:1) Terpolymer of Example ⁴C11 Alkylethoxylated surfactant containing 9 ethoxy groups. ⁵1,3bis(methylamine)-cyclohexane. ⁶C10 Alkyl ethoxylated surfactantcontaining 8 ethoxy groups. ⁷1,3 pentane diamine.

Example 8

DMAEMA copolymer was prepared from DMAEMA (also known as DMAM), citricacid, water, and HEA alone or with AA. In particular, the HEA:DMAEMAcopolymer was made with two separate monomer feeds. DMAEMA wasneutralized by adding it to citric acid and water. HEA was mixed withwater. The two monomer mixtures, i.e., DMAEMA (neutralized with citricacid) and HEA, and the redox initiator components, namely sodiumpersulfate solution and sodium metabisulfite solution were meteredseparately but simultaneously over 2.5 hours at 85° C. to a reactionvessel. Then the combined ingredients were held for 1 hour and extrainitiator was added to further reduce residual monomer. Then thecombined ingredients were held for another hour. The reactiontemperature was 85EC and there was 27.0% active polymer.

The residual monomer values were measured with HPLC (high pressureliquid chromatography) at room temperature and measured after heating at80° C. in a phosphate buffer (pH=4.2) for several hours. The sampleafter heating at 80° C. would reveal the amount of monomer that was notpolymerized but bound to the polymer.

The polymer concentration of the analyzed samples was 1-5 mg/ml activepolymer. In the following Table, % initiator is based on weight percentof the monomers. All residual monomer values are parts per million basedon active content (polymer solids).

The presence of AA listed in Table 1 was most likely due to the acrylicacid present in the HEA (<1%) raw material as supplied or to a smallextent may be due to some hydrolysis of HEA.

The residual monomer values were as shown in TABLE A. All residualmonomer values are parts per million based on active content (polymersolids).

Further treatment with extra amount of initiator in this example wasable to reduce the residual monomer to <500 ppm (when heated at 80° C.for 4 hours).

In the Table A of this Example under the headings “Residual MonomerBefore Further Treatment: room temp (80° C./4 hrs)” and “ResidualMonomer After Further Treatment: room temp (80° C./4 hrs)”, the valuesoutside of parentheses are those in ppm based on active polymer measuredat room temperature before heaing and the values in parentheses arethose in ppm based on active polymer of the analyzed samples afterheating to 80° C. for four hours.

The results of these samples are shown in TABLES VI A and VI B. In thetables ND means non-detectable (less than 2 ppm).

TABLE VI A Results of Citric Acid Neutralized HEA:DMAEMA (3:1) CopolymerPrepared With Separate Monomer Feeds Residual Monomer Residual MonomerBefore Further After Further Monomer Treatment: room Treatment: roomInitiator pH temp (80° C./4 hrs) temp (80° C./4 hrs) 1) 2.1% DMAEMA =HEA = 6 (309) HEA = 8(83) Na₂S₂O₈ 5.2 DMAEMA = 5 (18) DMAEMA = 8 (ND) 2)0.6% HEA = 3.3 AA = 92 (1630) AA = 27 (119) Na₂S₂O₅ MAA = ND (ND) MAA =ND (ND)

TABLE VI B Results of Citric Acid Neutralized HEA:DMAEMA (3:1) CopolymerPrepared With Separate Monomer Feeds % SOLID B.V. pH (Theoretical Value)(As is, 25° C.) (as is, 25° C.) Appearance 32.95% 1070 cps 3.95 Clear(#31v, 60 rpm) yellow solution

It should be understood that embodiments other than those specificallydisclosed may come within the spirit and scope of the present invention.Thus, it is submitted that the present invention is not limited by theforegoing description. Rather the present invention is defined by theclaims appended hereto.

1. A method of cleaning hard bathroom surfaces comprising applying tosaid surfaces a foam cleaner comprising a foaming agent and a polymer:the polymer comprising: units capable of having a cationic charge at apH of from about 4 to about 12; provided that said polymer has anaverage cationic charge density of 2.77 or less units per 100 daltonsmolecular weight at a pH of from about 4 to about
 12. 2. The methodaccording to claim 1, further comprising a) units capable of having acationic charge at a pH of from about 4 to about 12; provided that saidsuds/foam stabilizer has an average cationic charge density from about0.01 to about 2.75 units per 100 daltons molecular weight at a pH offrom about 4 to about
 12. 3. The method according to claim 1, furthercomprising: ii) one or more units having one or more hydroxyl groups,provided that the polymer has a hydroxyl group density of from about 0.5or less as measured by the Hydroxyl Group Density Equation as outlinedin greater detail below; and/or iii) one or more units having one ormore hydrophobic groups, preferably the hydrophobic groups are selectedfrom the group consisting of non-hydroxyl groups, non-cationic groups,non-anionic groups, non-carbonyl groups, and/or non-H-bonding group,more preferably the hydrophobic groups are selected from the groupconsisting of alkyls, cycloalkyls, aryls, alkaryls, aralkyls andmixtures thereof.
 4. The method according to claim 1, wherein saidpolymer further comprises: iv) units capable of having an anionic chargeat a pH of from about 4 to about 12; v) units capable of having ananionic charge and a cationic charge at a pH of from about 4 to about12; vi) units having no charge at a pH of from about 4 to about 12; andvii) mixtures of units (iv), (v), (vi), and (vii).
 5. The method polymeraccording to claim 2, wherein said polymer has an average molecularweight of from about 1,000 to about 2,000 daltons.
 6. The method polymeraccording to claim 1, wherein said polymer has an average cationiccharge density of about 0.75 to about 2.25 units per 100 daltonsmolecular weight at a pH of about 4 to about 12 and a molecular weightof about 10,000 to about 100,000 daltons.
 7. A method of cleaning hardbathroom surfaces comprising applying to said surfaces a foam cleanercomprising a foaming agent and a polymer: the polymer comprising: A. atleast one cationic monomeric unit A having a Formula I:

wherein R¹ is H or an alkyl having 1 to 10 carbon atoms, R² is a moietyselected from the group consisting of

wherein R³ is selected from the group consisting of

a is an integer from 0 to 16; b is an integer from 2 to 10; c is aninteger from 2 to 10; d is an integer from 1 to 100; R⁴ and R⁵ areindependently selected from the group consisting of —H, and

R⁵ is independently selected from the group consisting of a bond and analkylene having 1 to 18 carbon atoms; R⁹ and R¹⁹ are independentlyselected from the group consisting of —H, alkyl having 1 to 10 carbonatoms; R¹² and R¹³ are independently selected from the group consistingof H and alkyl having from 1 to 10 carbon atoms;

wherein x is an integer from 2 to 10; B. at least one monomeric unit Bselected from the group consisting of: a monomeric unit of Formula IV

wherein R²⁰ is selected from the group consisting of H and CH₃; R²¹ isselected from the group consisting of:

wherein e is an integer from 3 to 25;—O—(CH₂)_(f)—CH₃ wherein f is an integer from 0 to 25;

wherein g is an integer from 1 to 100, h is an integer from 1 to 100,R²³ is —H, —CH₃ or —C₂H₅, R²⁴ is —CH₃ or —C₂H₅;

wherein j is an integer from 1 to 25;

wherein k is an integer from 1 to 25;

—NH—(CH₂)_(m)—NH₂.HCl, wherein m is an integer from 1 to 25; and apolyhydroxy monomeric unit of Formula VI:

wherein n is an integer from 1 to 50; and C. optionally at least onemonomeric unit C selected from the group consisting of:

wherein R²⁵ is —H or —CH₃,

wherein R²⁶ is —H or CH₃.
 8. The method of claim 7, wherein said polymercomprises at least one said monomeric unit A, at least one saidmonomeric unit B and at least one said monomeric unit C.
 9. The methodof claim 7, wherein said at least one monomeric unit A is selected fromthe group consisting of:

wherein R³⁰ is H or —CH₃, wherein R³¹ is a bond or

and R³² and R³³ are —CH₃ or —C₂H₅.
 10. The method of claim 9, whereinsaid polymer is a terpolymer, said at least one monomeric unit B isselected from the group consisting of:

wherein R³⁸ is selected from the group consisting of H and CH₃ and R⁴⁰is selected from the group consisting of —CH₂CH₂—OH and

and isomers thereof, said terpolymer comprising said at least onemonomeric unit C, wherein the molar ratio of said monomeric unit A:monomeric unit B: monomeric unit C is 1 to 9:1 to 9:1 to 6 respectively.11. The method polymer of claim 7, wherein the at least one monomericunit B has the formula:

wherein q ranges from 1 to
 12. 12. The method of claim 11, wherein thepolymer is a terpolymer, said at least one monomeric unit A is selectedfrom the group consisting of:

wherein R¹⁰ is H or CH₃, R¹¹ is a bond or

and R¹² and R¹³ are —CH₃ or —C₂H₅, and said monomer comprises said atleast one monomeric unit C.
 13. The method of claim 12, wherein themolar ratio of monomeric unit A: monomeric unit B: monomeric unit Cranges from 1 to 9:1 to 9:1 to 3 respectively.
 14. The method of claim7, wherein said at least one monomeric unit A has a formula selectedfrom the group consisting of:


15. The method of claim 7, wherein said at least one monomeric unit Ahas a formula selected from the group consisting of:


16. The method of claim 7, wherein said at least one monomeric unit B isselected from the group consisting of:

wherein n is an integer from 1 to 50,


17. The method of claim 7, selected from the group consisting of:poly(HEA-co-DMAM-co-AA) terpolymer, poly(HPA-co-DMAM-co-AA) terpolymer,and poly(PEG-acrylate-co-DMAM-co-AA) terpolymer.
 18. The polymer methodof claim 7, selected from the group consisting of: poly(HEA-co-DMAM)copolymer, poly(DMAM-co-butylvinylether) copolymer andpoly(2-diethylaminoethylvinyl ether-co-ethyleneglycol monovinyl ether).19-41. (canceled)